Oxycarbonitride Phosphors and Light Emitting Devices Using the Same

ABSTRACT

Disclosed herein is a novel family of oxycarbonitride phosphor compositions and light emitting devices incorporating the same. Within the sextant system of M-Al—Si—O—N—C-Ln and quintuplet system of M-Si—O—N—C-Ln (M=alkaline earth element, Ln=rare earth element), the phosphors are composed of either one single crystalline phase or two crystalline phases with high chemical and thermal stability. In certain embodiments, the disclosed phosphor of silicon oxycarbonitrides emits green light at wavelength between 530-550 nm. In further embodiments, the disclosed phosphor compositions emit blue-green to yellow light in a wavelength range of 450-650 nm under near-UV and blue light excitation.

CLAIM OF PRIORITY

This application claims priority to U.S. Provisional Application Nos.61/334,967, filed May 14, 2010, and 61/381,862, filed Sep. 10, 2010, thedisclosures of which are hereby incorporated by reference in theirentireties.

GOVERNMENT FUNDING

This invention was made with U.S. Government support under Department ofEnergy grant number DE-EE0003245. The U.S. Government may have certainrights in this invention.

STATEMENT REGARDING REFERENCES

All patents, publications, and non-patent references referred to hereinshall be considered incorporated by reference into this application intheir entireties.

BACKGROUND OF INVENTION

In recent years, R&D efforts have been intense on both LED chip andphosphors for phosphor-converted LED (pcLED), with the result that bothefficient high-power LEDs and efficient phosphors have beendemonstrated. However, a unique aspect of the phosphors operating inpcLED is that the phosphors are in close vicinity of the LED chip, andthe LEDs operate at high temperatures. Typical junction temperatures ofhigh power LEDs are in the range of 100° C.-150° C. At thesetemperatures, the crystal of the phosphor is at a high vibrationallyexcited state, causing the excitation energy to be directed to heatemission through lattice relaxation rather than to the desiredluminescence emission. Moreover, these lattice relaxations produceheating with vibrational excitation, and thereby further reduce theluminescence emission efficiency. This is a vicious cycle that precludessuccessful applications of existing phosphor materials. The pcLED lampfor general illumination application requires high optical energy flux(e.g., higher than 1 Watt/mm²) which causes additional heating by aStokes shift generated inside the phosphor crystals. Successfuldevelopment of pcLED lamps for general illumination, therefore, requiresphosphors that can operate highly efficiently at temperatures of 100°C.-150° C. The risk is that it is difficult both to achieve 90% quantumyield at room temperature and to have high thermal stability at 100°C.-150° C. The thermal stability of a phosphor's luminescence is anintrinsic property of the phosphor which is determined by thecomposition and the structure of the crystalline material.

Oxynitride phosphors have been considered for use in pcLEDs because oftheir excellent luminescence performance at high temperature rangementioned above. Prominent examples are the sialon-based phosphors whosehost crystals are constituted by chemical bonds of Si—N, Si—O, Al—N andAl—O as the backbone of the host crystal structure. Each of theoxynitride phosphors discovered so far comprises predominantly a singlecrystalline phase, and often a second phase is considered an “impurity”.However, phosphors are generally materials that permitnon-stoichiometric proportions and are usually heterogeneous. In thisinvention, a group of oxycarbonitride phosphor compositions aredemonstrated to be comprised of more than one unique crystalline phase,each of which fluoresces highly efficiently.

The introduction of carbon or carbide into crystalline phosphormaterials has previously been considered detrimental in luminescenceperformance. The often dark body color of various carbides may be asource of absorption or quenching of emission light. Also, residualunreacted carbide that remains after phosphor preparation utilizingcarbon or carbide processes can hinder the emission intensity of thephosphor.

Carbonitride phosphors are comprised of carbon, nitrogen, silicon,aluminum and/or other metals in the host crystal and one or more metaldopants as a luminescent activator. This class of phosphors recentlyemerged as a color converter capable of converting near UV (nUV) or bluelight to green, yellow, orange and red light. The host crystal ofcarbonitride phosphors is comprised of —N—Si—C— networks in which thestrong covalent bonds of Si—C and Si—N serve as the main structuralcomponents. Generically, the network structure formed by Si—C bonds hasa strong absorption in the entire visible light spectral region, andtherefore has been previously considered not suitable for use in hostmaterials for high efficiency phosphors. For example, in certainnitride-silicon-carbide phosphors in which Ce³⁺ is the dopant, theelectronic interaction between Ce³⁺ and the —N—Si—C— networks results ina strong absorption in 400-500 nm wavelengths, making the phosphor lessreflective in that particular spectral region of visible light. Thiseffect is detrimental to achieving a phosphor having a high emissionefficiency.

It has now been discovered that in certain oxycarbonitride phosphorcompositions, carbide actually enhances, rather than quenches, theluminescence of a phosphor, in particular at relatively hightemperatures (e.g. 200° C.-400° C.). The invention demonstrates that thereflectance of certain oxycarbonitride phosphors in the wavelength rangeof visible light decreases as the amount of carbide increases. Thesecarbide-containing phosphors have excellent thermal stability ofemission and high emission efficiency.

SUMMARY OF INVENTION

In certain embodiments, the present invention is directed to a novelfamily of oxycarbonitride phosphors expressed by:

M(II)_(a)Si_(b)O_(c)N_(d)C_(e):A   (1)

wherein 6<a<8, 8<b<14, 13<c<17, 5<d<9, and 0<e<2, preferably 6.5<a<7.5,8.5<b<12.5, 14<c<16, 6<d<7.5, and 0<e<1. M(II) comprises at least onedivalent cation, and may be selected from the group including Be, Mg,Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, Cd and other divalent transition metalions. A comprises a luminescence activator doped in the crystalstructure at a concentration level from about 0.001 mol % to about 20mol %, preferably from about 0.1 mol % to about 10 mol %, relative toM(II). A can be at least one metal ion selected from the group includingCe, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi, Sb,preferably Eu²⁺, Ce³⁺, Tb³⁺, Yb²⁺and Mn²⁺.

In certain embodiments, the present invention is directed to a novelfamily of oxycarbonitride phosphors expressed by:

M(II)₇Al_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y):A   (2)

wherein 0<x<12, 0<y<x, and 0<x+y<12. M(II) comprises at least onedivalent cation, and may be selected from the group including Be, Mg,Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, Cd and other divalent transition metalions. A comprises a luminescence activator doped in the crystalstructure at a concentration level from about 0.001 mol % to about 20mol %, preferably from about 0.1 mol % to about 10 mol %, relative toM(II). A can be at least one metal ion selected from the group includingCe, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi, Sb,preferably Eu²⁺, Ce³⁺, Yb²+and Mn²+.

In certain embodiments, the present invention is directed to a novelfamily of oxycarbonitride based phosphors expressed by:

M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y):A   (3)

wherein 0<x≦12, 0<x+y≦12, and 0<y<x. M(II) comprises at least onedivalent cation, and may be selected from the group including Be, Mg,Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, Cd and other divalent transition metalions. M(III) comprises at least one trivalent cation, and may beselected from the group including B, Al, Ga, In, Sc, Y, La and Gd, andother trivalent metal ions. A comprises a luminescence activator dopedin the crystal structure at the concentration level of from about 0.001mol % to about 20 mol %, preferably from about 0.1 mol % to about 10 mol%, relative to M(II). A can be at least one metal ion selected from thegroup including Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn,Bi, Sb, preferably Eu²⁺, Ce³⁺, Tb³⁺, Yb²⁺ and Mn²⁺.

In certain embodiments, the present invention is directed to a novelfamily of oxycarbonitride based phosphors expressed by:

M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x±3δ/2)N_(x∓δ-y)C_(y):A   (4)

and

M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x±δ/2)N_(x∓δ-y)C_(y±δ/2):A   (4a)

wherein 0<x<12, 0≦y<x, 0<x+y≦12, 0<}≦3, and δ<x+y. M(II) comprises atleast one divalent cation, and may be selected from the group includingBe, Mg, Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, Cd and other divalent transitionmetal ions. M(III) comprises at least one trivalent cation, and may beselected from the group including B, Al, Ga, In, Sc, Y, La and Gd, andother trivalent metal ions. A comprises a luminescence activator dopedin the crystal structure at a concentration level from about 0.001 mol %to about 20 mol %, preferably from about 0.1 mol % to about 10 mol %,relative to M(II) and M(I). A can be at least one ion .selected from thegroup including Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn,Bi, Sb, preferably Eu²⁺, Ce³⁺, Tb³⁺, Yb²⁺ and Mn²⁺.

In certain embodiments, the present invention is directed to a novelfamily of oxycarbonitride based phosphors expressed by:

M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±3δ/2)N_(x∓δ-z)C_(z):A  (5)

and

M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±δ/2)N_(x∓δ-z)C_(z±δ/2):A  (5a)

wherein 0<x<12, 0≦y<x, 0<z<x, 0<x+y+z≦12, z<x+δ, and 0<δ≦3. M(II)comprises at least one divalent cation, and may be selected from thegroup including Be, Mg, Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, Cd and otherdivalent transition metal ions. M(I) comprises at least one monovalentcation, and may be selected from the group including Li, Na, K, Rb, Cu,Ag and Au. M(III) comprises at least one trivalent cation, and may beselected from the group including B, Al, Ga, In, Sc, Y, La and Gd, andother trivalent metal ions. A comprises a luminescence activator dopedin the crystal structure at a concentration level from about 0.001 mol %to about 20 mol %, preferably from about 0.1 mol % to about 10 mol %,relative to M(II) and M(I). A can be at least one ion selected from thegroup including Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn,Bi, Sb, preferably Eu²⁺, Ce³⁺, Tb³⁺, Yb²⁺ and Mn²⁺.

In certain embodiments, the present ‘invention is directed to a novelfamily of oxycarbonitride based phosphors expressed by:

M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±3δ/2-v/2)N_(x∓δ-z)C_(z)H_(v):A  (6)

and

M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z))_(25-x±δ/2-v/2)N_(x∓δ-z)C_(z±δ/2)H_(v):A  (6a)

wherein 0<x<12, 0≦y<1, 0<z<x, z<x+δ, 0<δ≦3, 0≦v<1, and 0<x+y+z≦12. M(II)comprises at least one divalent cation, and may be selected from thegroup including Be, Mg, Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, Cd and otherdivalent transition metal ions. M(I) comprises at least one monovalentcation, and may be selected from the group including Li, Na, K, Rb, Cu,Ag and Au. M(III) comprises at least one trivalent cation, and may beselected from the group including B, Al, Ga, In, Sc, Y, La and Gd, andother trivalent metal ions. H comprises at least one monovalent anion,and may be selected from the group including F, Cl, Br and I. Acomprises luminescence activator doped in the crystal structure at aconcentration level from about 0.001 mol % to about 20 mol %, preferablyfrom about 0.1 mol % to about 10 mol %, relative to M(II) and M(I). Acan be at least one ion selected from the group including Ce, Pr, Nd,Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi, Sb, preferably Eu²⁺,Ce³⁺, Tb³⁺, Yb²⁺ and Mn²⁺.

In some embodiments, the present invention is directed to a composition(1) comprising a phosphor having the formulaM(II)_(a)Si_(b)O_(c)N_(d)C_(e):A, wherein: 6<a<8, 8<b<14, 13<c<17,5<d<9, and 0<e<2; M(II) comprises at least one divalent cation; and Acomprises a luminescence activator doped in the host crystal of thephosphor. In some embodiments, M(II) comprises at least one divalentcation selected from the group consisting of Be, Mg, Ca, Sr, Ba, Cu, Co,Ni, Pd, Zn, and Cd. In further embodiments, M(II) comprises two or moredifferent divalent cations. In certain embodiments, A comprises aluminescence activator selected from the group consisting of Ce, Pr, Nd,Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi, and Sb. In furtherembodiments, A is doped in the host crystal of the phosphor at aconcentration level of from about 0.001 mol % to about 20 mol % relativeto M(II). The mol % of A can be adjusted in increments of .0001 withinthis range. In some embodiments, A is doped in the host crystal of thephosphor at a concentration level of from about 0.01 mol % to about 10mol %. In further embodiments, A is doped in the host crystal of thephosphor at a concentration level of from about 0.10 mol % to about 5rnol%.

In certain embodiments, the phosphor of composition (1) comprises afirst crystalline phase. In further embodiments, the first crystallinephase is an orthorhombic crystal system or a triclinic crystal system.In some embodiments, it is possible that the same first crystallinephase can be classified as either orthorhombic or triclinic with similarcertainty. In some embodiments, the phosphor consists of only a singlecrystalline phase. In certain embodiments, the phosphor does notcomprise any other crystalline phase. In other embodiments, the phosphorcomprises at least a first crystalline phase and a second crystallinephase. In some embodiments, the first crystalline phase is anorthorhombic crystal system and the second crystalline phase is atriclinic crystal system belonging to space group P1 (No. 1). In otherembodiments, the first crystalline phase is a triclinic crystal systemand the second crystalline phase is a triclinic crystal system belongingto space group P1 (No. 1) which may be different from the firstcrystalline phase.

In some embodiments, the phosphor composition (1) comprises acrystalline phase that is an orthorhombic crystal system, wherein: theunit cell parameter a of the host crystal is from about 11.071 Å toabout 11.471 Å; the unit cell parameter b of the host crystal is fromabout 8.243 Å to about 8.643 Å; and the unit cell parameter c of thehost crystal is from about 7.667 Å to about 8.067 Å. Within each ofthese ranges, the unit cell parameters can vary in increments of 0.001.In some embodiments, the unit cell parameter a of the host crystal isfrom about 11.171 Å to about 11.371 Å; the unit cell parameter b of thehost crystal is from about 8.343 Å to about 8.543 Å; and the unit cellparameter c of the host crystal is from about 7.767 Å to about 7.967 Å:In other embodiments, the unit cell parameter a of the host crystal isfrom about 11.271 Å to about 11.371 Å; the unit cell parameter b of thehost crystal is from about 8.443 Å to about 8.543 Å; and the unit cellparameter c of the host crystal is from about 7.867 Å to about 7.967 Å.In other embodiments, the unit cell parameter a of the host crystal isfrom about 11.221 Å to about 11.321 Å; the unit cell parameter h of thehost crystal is from about 8.393 Å to about 8.493 Å; and the unit cellparameter c of the host crystal is from about 7.817 Å to about 7.917 Å.In preferred embodiments, the unit cell parameter a of the host crystalis from about 11.271 Å to about 11.301 Å; the unit cell parameter b ofthe host crystal is from about 8.383 Å to about 8.453 Å; and the unitcell parameter c of the host crystal is from about 7.807 Å to about7.907 Å.

In other embodiments, the phosphor composition (1) comprises acrystalline phase that is a triclinic crystal system, wherein: the unitcell parameter a of the host crystal is from about 11.049 Å to about11.449 Å; the unit cell parameter b of the host crystal is from about8.231 Å to about 8.631 Å; the unit cell parameter c of the host crystalis from about 7.662 Å to about 8.062 Å; the unit cell parameter α of thehost crystal is from about 87 degrees to about 93 degrees; the unit cellparameter β of the host crystal is from about 87 degrees to about 93degrees; and the unit cell parameter γ of the host crystal is from about87 to about 93 degrees. Within each of the ranges for unit cellparameters a, b, and c, the unit cell parameter can vary in incrementsof 0.001. Within the ranges for unit cell parameters α, β, and γ, theunit cell parameter can vary in increments of 0.01. In some embodiments,the unit cell parameter a of the host crystal is from about 11.149 Å toabout 11.349 Å; the unit cell parameter b of the host crystal is fromabout 8.331 Å to about 8.531 Å; the unit cell parameter c of the hostcrystal is from about 7.762 Å to about 7.962 Å; the unit cell parameterα of the host crystal is from about 89 degrees to about 91 degrees; theunit cell parameter β of the host crystal is from about 89 degrees toabout 91 degrees; and the unit cell parameter γ of the host crystal isfrom about 89 to about 91 degrees. In some embodiments, the unit cellparameter a of the host crystal is from about 11.249 Å to about 11.349Å; the unit cell parameter b of the host crystal is from about 8.431 Åto about 8.531 Å; the unit cell parameter c of the host crystal is fromabout 7.862 Å to about 7.962 Å; the unit cell parameter α of the hostcrystal is from about 89.5 degrees to about 90.5 degrees; the unit cellparameter βof the host crystal is from about 89.5 degrees to about 90.5degrees; and the unit cell parameter γ of the host crystal is from about89.5 to about 90.5 degrees. In some embodiments, the unit cell parametera of the host crystal is from about 11.199 Å to about 11.299 Å; the unitcell parameter b of the host crystal is from about 8.381 Å to about8.481 Å; the unit cell parameter c of the host crystal is from about7.812 Å to about 7.912 Å; the unit cell parameter α of the host crystalis from about 89.5 degrees to about 90.5 degrees; the unit cellparameter β of the host crystal is from about 89.5 degrees to about 90.5degrees; and the unit cell parameter γ of the host crystal is from about89.5 to about 90.5 degrees. In preferred embodiments, the unit cellparameter α of the host crystal is from about 89.5 degrees to about 89.9degrees; the unit cell parameter β of the host crystal is from about89.5 degrees to about 89.9 degrees; and the unit cell parameter γ of thehost crystal is from about 89.5 to about 89.9 degrees.

In certain embodiments, the phosphor composition (I) further comprisesone or more additional phosphors. In some embodiments, the phosphorcomposition further comprises at least one phosphor selected from thegroup consisting of: Ca_(1-x)Al_(x−xy)Si_(1-x+xy)N_(2-x−xy)C_(xy):A;Ca_(1-x−z)Na_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A;M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A;M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2w/3)C_(xy)O_(w-v/2)H_(v):A;andM(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy−2w/3-v/3)C_(xy)O_(w)H_(v):A;wherein 0<x<1, 0<y<1, 0≦z<1, 0≦v<1, 0<w<1, x+z<1, x>xy+z, v/2≦w,x−xy-2w/3-v/3<2, and 0<x−xy−z<1; M(II) is at least one divalent cation;M(I) is at least one monovalent cation; M(III) is at least one trivalentcation; H is at least one monovalent anion; and A is a luminescenceactivator.

In certain embodiments, the present invention is directed to acomposition (2) comprising a phosphor having the formulaM(II)₇Al_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y):A, wherein 0<x≦12, 0<y<x,and 0<x+y<12; M(II) comprises at least one divalent cation; and Acomprises a luminescence activator doped in the crystal structure. Incertain embodiments, M(II) comprises at least one divalent cationselected from the group consisting of Be, Mg, Ca, Sr, Ba, Cu, Co, Ni,Pd, Zn, and Cd. In some embodiments, M(II) comprises two or moredifferent divalent cations. In further embodiments, A comprises aluminescence activator that is selected from the group consisting of Ce,Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi, and Sb. In someembodiments, A is doped in the host crystal of the phosphor at aconcentration level of 0.001 mol % to 20 mol % relative to M(II). Themol % of A can be adjusted in increments of 0.0001 within this range. Insome embodiments, A is doped in the host crystal of the phosphor at aconcentration level of from about 0.01 mol % to about 10 mol %. Infurther embodiments, A is doped in the host crystal of the phosphor at aconcentration level of from about 0.10 mol % to about 5 mol %.

In some embodiments, the phosphor of composition (2) comprises acrystalline phase that is a triclinic crystal system belonging to spacegroup P1 (No. 1). In some embodiments, the phosphor consists of only asingle crystalline phase. In certain embodiments, the phosphor does notcomprise any other crystalline phase. In other embodiments, the phosphorcomprises at least a first crystalline phase and a second crystallinephase. In certain embodiments, the first crystalline phase is anorthorhombic crystal system and the second crystalline phase is atriclinic crystal system belonging to space group P1 (No. 1). In otherembodiments, the first crystalline phase is a triclinic crystal systemand the second crystalline phase is a triclinic crystal system belongingto space group P1 (No. 1) which may be different than the firstcrystalline phase. In some embodiments, it is possible for the samecrystalline phase to be classified as either orthorhombic or triclinicwith similar certainty.

In certain embodiments, the phosphor composition (2) comprises acrystalline phase that is a triclinic crystal system belonging to spacegroup P1 (No. 1), wherein the unit cell parameter a of the host crystalis from about. 6.9011 Å to about 7.3011 Å; the unit cell parameter b ofthe host crystal is from about 7.0039 Å to about 7.4039 Å; the unit cellparameter c of the host crystal is from about 7.0728 Å to about 7.4728Å; the unit cell parameter α of the host crystal is from about 85degrees to about 92 degrees; the unit cell parameter β of the hostcrystal is from about 81 degrees to about 88 degrees; and the unit cellparameter γ of the host crystal is from about 72 degrees to about 79degrees. Within each of the ranges for unit cell parameters a, b, and c,the unit cell parameter can vary in increments of 0.0001. Within theranges for unit cell parameters α, β, and γ, the unit cell parameter canvary in increments of 0.001. In certain embodiments, the unit cellparameter a of the host crystal is from about 7.0011 Å to about 7.2011Å; the unit cell parameter b of the host crystal is from about 7.1039 Åto about 7.3039 Å; the unit cell parameter c of the host crystal is fromabout 7.1728 Å to about 7.3728 Å; the unit cell parameter α of the hostcrystal is from about 87 degrees to about 90 degrees; the unit cellparameter β of the host crystal is from about 83 degrees to about 86degrees; and the unit cell parameter γ of the host crystal is from about74 degrees to about 77 degrees. In certain embodiments, the unit cellparameter α of the host crystal is from about 7.0511 Å to about 7.1511Å; the unit cell parameter b of the host crystal is from about 7.1539 Åto about 7.2539 Å; the unit cell parameter c of the host crystal is fromabout 7.2228 Å to about 7.3228 Å; the unit cell parameter α of the hostcrystal is from about 88.431 degrees to about 89.431 degrees; the unitcell parameter β of the host crystal is from about 84.415 degrees toabout 84.515 degrees; and the unit cell parameter γ of the host crystalis from about 75.593 degrees to about 76.593 degrees. En preferredembodiments, the unit cell parameter a of the host crystal is from about88.9 degrees to about 89.9 degrees; the unit cell parameter 13 of thehost crystal is from about 84.5 degrees to about 85.0 degrees; and theunit cell parameter y of the host crystal is from about 75.6 to about76.5 degrees.

In certain embodiments, the phosphor composition (2) comprises one ormore additional phosphors. In some embodiments, the composition furthercomprises at least one phosphor selected from the group consisting of:Ca_(1-x)Al_(x−xy)Si_(1-x+xy)N_(2-x−xy)C_(xy):ACa_(1-x−z)Na_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A;M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A;M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2w/3)C_(xy)O_(2-v/2)H_(v):A;andM(II)_(1-x−z)M(I)_(z)M(III)_(z−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2-w/3-v/3)C_(xy)O_(w)H_(v):A;wherein 0<x<1, 0<y<1, 0≦z<1, 0≦v<1, 0<w<1, x+z<1, x>xy+z, v/2≦w,x−xy-2w/3-v/3<2, and 0<x−xy−z<1; M(II) is at least one divalent cation;M(I) is at least one monovalent cation; M(III) is at least one trivalentcation; H is at least one monovalent anion; and A is a luminescenceactivator.

In certain embodiments, the present invention is directed to acomposition (3, 4, 4a, 5, 5a, 6, or 6a) comprising a phosphor having aformula selected from the group consisting of:

(a) M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y):A, wherein 0<x≦12.0<x+y≦12, and 0<y<x;

(b) M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x±3δ/2)N_(x∓δ-y)C_(y):A; wherein0<x<12, 0≦y<x, 0<x+y≦12, 0<δ≦3, and δ<x+y;

(c) M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x±δ/2)N_(x∓δ-y)C_(y±δ/2):A;wherein 0<x12, 0≦y<x, 0<x+y≦12, 0<}≦3, and δ<x+y;

(d)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±3δ/2)N_(x∓δ-z)C_(z):A;wherein 0<x12, 0≦y<x, 0<z<x, 0<x+y+z≦12, z<x+δ, and 0<δ≦3;

(e)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±δ2)N_(x∓δ-z)C_(z±δ/2):A,wherein 0<x12, 0≦y<x, 0<z<x, 0<x+y+z≦12, z<x+δ, and 0<δ≦3;

(f)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±δ/2-v/2)N_(x∓δ-z)C_(z)H_(v):A;wherein 0<x<12, 0≦y<1, 0<z<x, z<x+δ, 0<δ≦3, 0≦v<1, and 0<x+y+z≦12; and

(g)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±δ/2-v/2)N_(x∓δ-z)C_(z±δ/2)H_(v):A,wherein 0<x<12, 0≦y<1, 0<z<x, z<x+δ, 0<δ≦3, 0≦v<1, and 0<x+y+z≦12;

wherein:

M(II) comprises at least one divalent cation;

M(I) comprises at least one monovalent cation;

M(III) comprises at least one trivalent cation;

H comprises at least one monovalent anion; and

A comprises a luminescence activator doped in the crystal structure.

In certain embodiments of the composition (3, 4, 4a, 5, 5a, 6, or 6a),M(II) comprises at least one divalent cation selected from the groupconsisting of Be, Mg, Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, and Cd; M(III)comprises at least one trivalent cation selected from the groupconsisting of B, Al, Ga, In, Sc, Y, La and Gd; M(1) comprises at leastone monovalent cation selected from the group consisting of Li, Na, K,Rb, Cu, Ag and Au; and H comprises at least one monovalent anionselected from the group consisting of F, Cl, Br and I. In someembodiments, A comprises at least one luminescence activator selectedfrom the group consisting of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,Yb, Lu, Mn, Bi, and Sb. In further embodiments, A is doped in the hostcrystal of the phosphor at the concentration level of 0.001 mol % to 20mol % relative to M(II) and M(I). The mol % of A can be adjusted inincrements of 0.0001 within this range. In some embodiments, A is dopedin the host crystal of the phosphor at a concentration level of fromabout 0.01 mol % to about 10 mol %. In further embodiments, A is dopedin the host crystal of the phosphor at a concentration level of fromabout 0.10 mol % to about 5 mol %.

In some embodiments, the phosphor composition (3, 4, 4a, 5, 5a, 6, or6a) comprises a crystalline phase that is a triclinic crystal systembelonging to space group P1 (No.1). In some embodiments, the phosphorconsists of only a single crystalline phase. In certain embodiments, thephosphor does not comprise any other crystalline phase. In otherembodiments, the phosphor comprises at least a first crystalline phaseand a second crystalline phase. In certain embodiments, the firstcrystalline phase is an orthorhombic crystal system and the secondcrystalline phase is a triclinic crystal system belonging to space groupP1 (No. 1). In other embodiments, the first crystalline phase is atriclinic crystal system and the second crystalline phase is a tricliniccrystal system belonging to space group P1 (No. 1) that may be differentfrom the first crystalline phase. In some embodiments, it is possiblefor the same crystalline phase to be classified as either orthorhombicor triclinic with similar certainty.

In certain embodiments, the phosphor composition (3, 4, 4a, 5, 5a, 6, or6a) further comprises one or more additional phosphors. In someembodiments, the composition further comprises at least one phosphorselected from the group consisting of:Ca_(1-x)Al_(x−xy)Si_(1-x+xy)N_(2-x−xy)C_(xy):A;Ca_(1-x−z)Na_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A;M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A;M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2w/3)C_(xy)O_(w-v/2)H_(v):A;andM(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2w/3-v/3)C_(xy)O_(w)H_(v):A;wherein 0<x<1, 0<y<1, 0≦z<1, 0≦v<1, 0<w<1, x+z−1, x>xy+z, v/2≦w,x−xy-2w/3-v/3<2, and 0<x−xy−z<1; M(II) is at least one divalent cation;M(I) is at least one monovalent cation; M(III) is at least one trivalentcation; H is at least one monovalent anion; and A is a luminescenceactivator.

In certain embodiments, the present invention is directed to acomposition comprising a phosphor that comprises at least one carbonatom; at least one divalent cation M(II); at least one oxygen atom; andat least one nitrogen atom; wherein the phosphor comprises a firstcrystalline phase that is either an orthorhombic crystal system or atriclinic crystal system. In some embodiments, M(II) comprises at leastone divalent cation selected from the group consisting of Be, Mg, Ca,Sr, Ba, Cu, Co, Ni, Pd, Zn, and Cd. In some embodiments, the phosphorfurther comprises a luminescence activator A doped in the host crystalof the phosphor at the concentration level of 0.001 mol % to 20 mol %relative to M(II). The mol % of A can be adjusted in increments of0.0001 within this range. In some embodiments,. A is doped in the hostcrystal of the phosphor at a concentration level of from about 0.01 mol% to about 10 mol %. In further embodiments, A is doped in the hostcrystal of the phosphor at a concentration level of from about 0.10 mol% to about 5 mol %. In further embodiments, the phosphor furthercomprises at least a second crystalline phase. In some embodiments, thesecond crystalline phase is a triclinic crystal system belonging tospace group P1 (No.1). In certain embodiments, the phosphor emits lightin a single emission spectrum from about 400 nm to about 650 nm whenexcited by a light source.

In certain embodiments, the present invention is directed to a lightemitting device comprising: a light source emitting a first luminescencespectrum; and a phosphor composition, which, when irradiated with lightfrom the light source, emits light having a second luminescencespectrum; wherein the phosphor composition comprises at least onephosphor selected from the group consisting of:

(a) M(II)_(a)Si_(b)O_(c)N_(d)C_(e):A, wherein 6<a<8, 8<b<14, 13<c<17,5<d<9, 0<e<2;

(b) M(II)₇Al_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y):A, wherein 0<x≦12,0<y<x, and 0<x+y≦12,

(c) M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y):A, wherein 0<x≦12,0<x+y≦12, and 0<y<x;

(d) M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x±δ/2)N_(x∓δ-y)C_(y):A, wherein0<x<12, 0≦y<x, 0<x+y≦12, 0<δ<3, and δ<x+y;

(e) M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x±δ/2)N_(x∓δ-y)C_(y±δ/2):A,wherein 0<x<12, 0≦y<x, 0<x+y≦12, 0<δ<3, and δ<x+y;

(f)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±3δ/2)N_(x∓δ-z)C_(z):A,wherein 0<x<12, 0≦y<x, 0<z<x, 0<x+y+z≦12, z<x+δ, and 0<δ<3;

(g)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±δ/2)N_(x∓δ-z)C_(z±δ/2):A,wherein 0<x<12, 0≦y<x, 0<z<x, 0<x+y+z≦12, z<x+δ, and 0<δ≦3;

(h)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±3δ/2)N_(x∓δ-z)C_(z)H_(v):A,wherein 0<x<12, 0≦y<1, 0<z<x, z<x+δ, 0<δ≦3, 0≦v<1, and 0<x+y+z≦12; and

(i)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±δ/2-v/2)N_(x∓δ-z)C_(z±δ-z)H_(v):A,wherein 0<x<12, 0≦y<1, 0<z<x, z<x+δ, 0<δ<3, 0≦v<1, and 0<x+y+z≦12;

wherein:

M(II) comprises at least one divalent cation;

M(I) comprises at least one monovalent cation;

M(III) comprises at least one trivalent cation;

H comprises at least one monovalent anion; and

A comprises a luminescence activator doped in the crystal structure.

In certain embodiments of the light emitting device, M(II) comprises atleast one divalent cation selected from the group consisting of Be, Mg,Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, and Cd; M(1) comprises at least onemonovalent cation selected from the group consisting of Li, Na, K, Rb,Cu, Ag and Au; M(III) comprises at least one trivalent cation selectedfrom the group consisting of B, Al, Ga, In, Sc, Y, La and Gd; Hcomprises at least one anion selected from the group consisting of F,Cl, Br and I; and A comprises at least one luminescence activtorselected from the group consisting of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb, Lu, Mn, Bi, and Sb. In some embodiments, A is doped inthe host crystal of the phosphor at the concentration level of 0.001 mol% to 20 mol % relative to M(II). The mol % of A can be adjusted inincrements of .0001 within this range. In some embodiments, A is dopedin the host crystal of the phosphor at a concentration level of fromabout 0.01 mol % to about 10 mol %. In further embodiments, A is dopedin the host crystal of the phosphor at a concentration level of fromabout 0.10 mol % to about 5 mol %.

In some embodiments, the first luminescence spectrum is from about 300nm to about 600 nm. In further embodiments, the first luminescencespectrum is from about 400 to about 550 nm. In some embodiments, thelight source is a light emitting diode or a laser diode. In certainembodiments, the device further comprises one or more additionalphosphors. In some embodiments, an additional phosphor emits red lightwhen excited by a light source. In certain embodiments, the lightemitting device further comprises at least a second phosphor having aformula selected from the group consisting ofCa_(1-x)Al_(x−xy)Si_(1-x+xy)N_(2-x−xy)C_(xy):A;Ca_(1-x−z)Na_(z)M(III)_(x−xy−z)Si_(1-x+y+z)N_(2-x−xy)C_(xy):A;M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A;M(II)_(1-x−z)M(I)_(z)M(III)_(z−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2w/3)C_(xy)O_(w-v/2)H_(v):A;andM(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2w/3-v/3)C_(xy)O_(w)H_(v):A;wherein 0<x<1, 0<y<1, 0≦z<1, 0≦v<1, 0<w<1, x+z<1, x>xy+z, v/2≦w,x−xy-2w/3-v/3<2, and xy+z, v/0<x−xy−z<1; M(II) is at least one divalentcation; M(I) is at least one monovalent cation; M(III) is at least onetrivalent cation; I-I is at least one monovalent anion; and A is aluminescence activator. In further embodiments, the light emittingdevice further comprises at least two additional phosphors.

In certain embodiments, the light emitting device further comprises atleast one additional phosphor that emits light having a peak inwavelength range from about 480 to about 660 nm when excited by a lightsource. In some embodiments, the device further comprise at least oneadditional phosphor that emits light having a peak in wavelength rangefrom about 520 to about 640 nm when excited by a light source. In someembodiments, the device emits white light. In certain embodiments, thedevice emits cool white light. In other embodiments, the device emitswarm white light. In further embodiments, the device emits green lighthaving a wavelength value from about 480 nm to about 600 nm. In otherembodiments, the device emits light having a wavelength value from about500 nm to about 590 nm. In still other embodiments, the device emitslight having a wavelength value from about 380 nm to about 750 nm. Infurther embodiments, the device emits light having a wavelength valuefrom about 400 nm to about 700 nm.

In certain embodiments, the device further comprises at least onephosphor selected from the group consisting of Ca_(1-x)Sr_(x)S:Eu²⁺(0≦x≦1), 3.5MgO.0.5MgF₂.GcO₂:Mn⁴⁺, Y₂O₂S:Eu³⁺, M₂Si₅N₈:Eu²⁺ (M=Ca, Sr,Ba), MAlSiN₃:Eu²⁺ (M=Ca, Sr), Y₂Si₄N₆C:Eu²⁺, CaSiN₂:Eu²⁺,Ca_(1-x)Sr_(x)Ga₂S4:Eu²⁺ (0≦x≦1),Ca_(1-x−y−z)Mg_(x)Sr_(y)Ba_(z)SiO₄:Eu²⁺ (0≦x≦1, 0≦y≦1, 0≦z≦1, x+y+z≦1),BaMgAl₁₀O₁₇:Eu²⁺,Mn²⁺, MYSi₄N₇:Eu²⁺ (M=Ca, Sr, Ba), β-sialon:Eu²⁺,MSi₂O₂N₂:Eu²⁺ (M=Ca, Sr, Ba), Ba₃Si₆O₁₂N₂:Eu²⁺, M₂Si₅N₈:Ce³⁺ (M=Ca, Sr,Ba), Y₂Si₄N₆C:Ce³⁺, α-sialon:Yb²⁺, (MSiO₃)_(m).(SiO₂)_(n):EU²⁺, X(M=Mg,Ca, Sr, Ba; X═F, Cl, Br, I; m is 1 or 0, and either (i) n>3 if m=1 or(ii) n=1 if m=0), MAl₂O₄:Eu²⁺ (M=Mg, Ca, Sr), BaMgAl₁₀O₁₇:Eu²⁺,Y₃Al₅O₁₂:Ce³⁺ (cerium-doped garnet type phosphor), and α-sialon:Eu²⁺.

Definitions

As used herein, “activator” refers to the atomic or ionic species thatemits light with the support of the host crystal. The activator may bedoped in the host crystal in a very small amount, as further describedherein. The activator can comprise a single element, such as, forexample and without limitation, Eu²⁺, or can comprise multiple elements(i.e. co-activators), such as, for example and without limitation, acombination of two or more of Eu²⁺, Ce³⁺, Tb³⁺, Yb²⁺ and Mn²⁺.

As used herein, a “phosphor composition” refers to a compositioncomprising a phosphor having the ratio of atoms specified for theparticular phosphor. It may or may not be stoichiometric proportions.Impurities and one or more crystalline phases may be present in thecomposition.

As used herein, “co-activator” refers to an additional activator in thesame host crystal.

As used herein, “dopant” refers to an atomic or ionic species that isdoped in a host crystal.

As used herein, “particle” refers to an individual crystal of phosphor.

As used herein, “grain” refers to an agglomeration, aggregation,polycrystalline or polymorph of phosphor particles, where the particlesare not easily separated as compared to phosphor particles of a powder.

As used herein, the term “phosphor” refers to a phosphor in anyappropriate form, such as a phosphor particle, a phosphor grain, orphosphor powder comprised of phosphor particles, grains, or acombination thereof.

As used herein, “light source” refers to any source of light capable ofexciting or irradiating the phosphors of the present invention,including without limitation a Group III-V semiconductor quantumwell-based light emitting diode, a laser diode, or a phosphor other thanthe phosphor of a light emitting device of the present invention. Thelight source of the present invention can either excite/irradiate thephosphor directly, or excite another system to thereby provide theexcitation energy for the phosphor indirectly.

Temperatures described herein for processes involving a substantial gasphase are of the oven or other reaction vessel in question, not of thereactants per se.

“White light,” as used herein, is light of certain chromaticitycoordinate values (e.g., Commission Internationale de l'Êclairage(CIE)), which are well-known in the art. Correlated color temperature ofa light source is the temperature of an ideal black-body radiator thatradiates light of comparable hue to that light source. Higher colortemperatures (5,000 K or more) are called cool colors (or “cool white”);lower color temperatures (2,700-3,000 K) are called warm colors (or“warm white”).

Throughout the specification, reference may be made to M(I), M(II), andM(III), where M(I) is at least one monovalent cation, M(II) is at leastone divalent cation, and M(III) is at least one trivalent cation. Inaddition to any values for these variables that may be given withrespect to a particular formulation, M(II) may be selected from thegroup consisting of Be, Mg, Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, and Cd; M(I)may be selected from the group consisting of Li, Na, K, Rb, Cu, Ag andAu; and M(III) is selected from the group consisting of B, Al, Ga, In,Sc, Y, La and Gd.

For the purposes of the examples described herein, the quantumefficiency (QE) was measured against the same internal standard sample.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. All technical and scientificterms used herein have the same meaning when used. It must be notedthat, as used herein and in the appended claims, the singular forms “a”,“and”, and “the” include plural references unless the context clearlydictates otherwise.

In the description of phosphor compositions, a conventional notation isused, wherein the chemical formula for the host crystal is given first,followed by a colon and the formula for the activator andco-activator(s). In certain instances in this specification where thestructure of a phosphor's host crystal is discussed, the activator(s)may not be included when referencing the phosphor's formulation.

BRIEF DESCRIPTION OF THE FIGURES

FIGS. 1A and 1B depict the XRD pattern of the phosphor compositions ofsamples 1.1a and 1.1b, respectively.

FIG. 2A depicts excitation (left curve) and emission (right curve)spectra of sample 1.1a. FIG. 2B depicts the emission spectrum of sample1.1b.

FIG. 3 depicts the thermal quenching profiles of the phosphorcompositions of samples 1.1a and 1.1b.

FIG. 4A depicts the excitation (left curve) and emission (right curve)spectra of sample 2.10. FIG. 4B depicts the XRD pattern of the phosphorcomposition of sample 2.10, which demonstrates a high proportion of atriclinic crystalline phase.

FIG. 5 depicts the thermal quenching characteristic of the phosphorcomposition of sample 2.10.

FIG. 6 depicts the XRD patterns of phosphor compositions of Example 2a.

FIGS. 7A and 7B each depict a further view of the XRD patterns ofphosphor compositions of Example 2a. FIG. 7A depicts a closer view inthe 2θ=31.0-32.6 range. FIG. 7B depicts a closer view in the2θ=28.0-28.8 range.

FIG. 8 depicts the excitation profiles (left curves) and emissionspectra (right curves) of the phosphor compositions of samples 2.7, 2.8,2.5, 2.10, and 2.13.

FIG. 9 depicts the thermal quenching profiles of two phosphorcompositions of Example 2a, samples 2.6 (carbon-free) and 2.5 (carboncontaining).

FIG. 10 depicts the XRD patterns of phosphor compositions of Example 2b.

FIG. 11 depicts a further view of the XRD patterns of phosphorcompositions of Example 2b.

FIG. 12 depicts the thermal quenching profile of the phosphorcomposition of sample 3.2.

FIG. 13 depicts the XRD patterns of phosphor compositions of Example 2c.

FIGS. 14A and 14B each depict a further view of the XRD patterns ofphosphor compositions of Example 2c. FIG. 14A depicts a closer view inthe 2θ=31.0-32.4 degree range. FIG. 14B depicts a closer view of the2θ=28.0-29.0 degree range.

FIG. 15 depicts the thermal quenching profiles of the phosphorcompositions of samples 5.1, 3.5, and 5.6.

FIG. 16 depicts the excitation profile (left curve) and emissionspectrum (right curve) of the phosphor composition of sample 5.9.

FIG. 17 depicts the reflection spectrum of the phosphor composition ofsample 5.9.

FIG. 18 depicts the excitation profile (left curve) and emissionspectrum (right curve) of the phosphor composition of sample 5.7.

FIG. 19 depicts the reflection spectrum of the phosphor composition ofsample 5.7.

FIG. 20 depicts one embodiment of the light emitting device of thepresent invention.

FIG. 21 depicts an embodiment of the light emitting device of thepresent invention.

FIG. 22 depicts an embodiment of the light emitting device of thepresent invention.

FIG. 23 depicts an embodiment of the light emitting device of thepresent invention.

FIG. 24 depicts the emission spectra of a pcLED (at varying operatingcurrents) packaged with the phosphor composition of sample 3.2 and ablue-emitting LED chip.

FIG. 25 depicts the luminance properties of the pcLED of Example 5b.

FIG. 26 depicts the emission spectrum of the pcLED of Example 5b. Theleft curve depicts the spectrum of the bare LED. The right curve depictsthe spectrum of the LED combined with the phosphor composition describedin Example 5b.

DETAILED DESCRIPTION

In certain embodiments, the present invention is directed to a novelfamily of oxycarbonitride phosphors expressed by:

M(II)_(a)Si_(b)O_(c)N_(d)C_(e):A   (1)

wherein 6<a<8, 8<b<14, 13<c<17, 5<d<9, 0<e<2; preferably 6.5<a<7.5,8.5<b<12.5, 14<c<16, 6<d<7.5, 0<e<1. M(II) comprises at least onedivalent cation, and may be selected from the group including Be, Mg,Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, Cd and other divalent transition metalions. A comprises a luminescence activator doped in the crystalstructure at the concentration level from about 0.001 mol % to about 20mol %, preferably from about 0.1 mol % to about 10 mol %, relative toM(II). A can be at least one metal ion selected from the group includingCe, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi, Sb,preferably Eu²⁺, Ce³⁺, Tb³⁺, Yb²⁺ and Mn²⁺.

These phosphors may contain a single crystalline phase, or, in thealternative, two or more crystalline phases. In certain embodiments, thephosphors of this family exhibit an orthorhombic crystalline phase or atriclinic crystal system. In other embodiments, the phosphors of thisfamily exhibit a high proportion of an orthorhombic crystalline phase.In other embodiments, these phosphors exhibit a second tricliniccrystalline phase belonging to space group P1 (No. 1).

In certain embodiments, the present invention is directed to a novelfamily of oxycarbonitride phosphors expressed by:

M(II)₇Al_(12-x−y)Si_(xy)O_(25-x)N_(x−y)C_(y):A   (2)

wherein 0<x≦12, 0<y<x, and 0<x+y≦12. M(II) comprises at least onedivalent cation, and may be selected from the group including Be, Mg,Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, Cd and other divalent transition metalions. A comprises a luminescence activator doped in the crystalstructure at the concentration level from about 0.001 mol % to about 20mol %, preferably from about 0.1 mol % to about 10 mol %, relative toM(II). A can be at least one metal ion selected from the group includingCe, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi, Sb,preferably Eu²⁺, Ce³⁺, Tb³⁴, Yb²⁺ and Mn²⁺.

Compositionally, the host crystalline substance of composition (2) wouldbe the product of the cross substitution of Si—N bonds for Al—O bonds inthe compound designated as Sr₇Al₁₂O₂₅. Sr₇Al₁₂O₂₅ is known to becrystallized in a trigonal crystal system with a space group of P-3. TheAl—O bonds of Sr₇Al₁₂O₂₅ could be replaced by the Si—N bonds from thenitrogen source Si₃N₄ and N₂ in a solid state reaction at hightemperature:

Sr₇Al₁₂O₂₅+xSi₃N₄→Sr₇Al_(12-x)Si_(x)O_(25-x)N_(x)

In theory, the structure of Sr₇Al₁₂O₂₅ remains when the substitution isin small portion, whereas the structure would change when a substantialamount of Al—O bonds are substituted by Si—N bonds. Furthermore, Al—Ncan be replaced by SiC, where Si occupies a site of Al, and C occupies asite of N in the starting composition expressed below:

M(II)₇Al_(12-x)Si_(x)O_(25-x)N_(x)+ySi₃N₄→M(II)₇Al_(12-x−y)Si_(x+y)N_(x−y)C_(y)

It is also possible for C to occupy a site occupied by O or both O and Nin the starting composition, i.e. M(II)₇Al_(12-x)Si_(x)O_(25-x)N_(x), toform a composition M(II)₇Al_(12-x−y)Si_(x)O_(25-x-2y)N_(x)C_(y) orM(II)₇Al_(12-x−y)Si_(x)O_(25-x−y)N_(x-2/3y)C_(y) which represents thatthe C can occupy either O sites or N sites or both.

In certain embodiments, the phosphors of this family exhibit a singletriclinic crystalline-’ phase belonging to space group P 1 (No. 1). Inother embodiments, the phosphors of this family exhibit a highproportion of a triclinic crystalline phase belonging to space group P1(No. 1). In other embodiments, these phosphors exhibit a secondcrystalline phase that can be classified as either an orthorhombiccrystal system or a triclinic crystal system.

In certain embodiments, the present invention is directed to a novelfamily of oxycarbonitride phosphors expressed by:

M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y):A   (3)

wherein 0<x≦12, 0<x+y≦12, and 0<y<x. M(II) comprises at least onedivalent cation, and may be selected from the group including Be, Mg,Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, Cd and other divalent transition metalions. M(III) comprises at least one trivalent cation, and may beselected from the group including B, Al, Ga, In, Sc, Y, La and Gd, andother trivalent metal ions. A comprises a luminescence activator dopedin the crystal structure at the concentration level from about 0.001 mol% to about 20 mol %, preferably from about 0.1 mol % to about 10 mol %,relative to M(II). A can be at least one metal ion selected from thegroup including Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn,Bi, Sb, preferably Eu²⁺, Ce³⁺, Tb³⁺, Yb²⁺ and Mn²⁺.

In certain embodiments, the present invention is directed to a novelfamily of oxycarbonitride based phosphors expressed by:

M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x±3δ/2)N_(x∓δ-y)C_(y):A   (4)

wherein 0<x<12, 0≦y<x, 0<x+y≦12, 0<δ<3, and δ<x+y. M(II) comprises atleast one divalent cation, and may be selected from the group includingBe, Mg, Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, Cd and other divalent transitionmetal ions. M(III) comprises at least one trivalent cation, and may beselected from the group including B, Al, Ga, In, Sc, Y, La and Gd, andother trivalent metal ions. A comprises a luminescence activator dopedin the crystal structure at a concentration level from about 0.001 mol %to about 20 mol %, preferably from about 0.1 mol % to about 10 mol %,relative to M(II). A can be at least one ion selected from the groupincluding Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi,Sb, preferably Eu²⁺, Ce³⁺, Tb³⁺, Yb²⁺ and Mn²⁺.

In the phosphor of composition (4), O and N atoms can be exchanged withone another in a ratio of 1.5 (oxygen) to 1 (nitrogen), or 3δ/2 (oxygen)to δ (nitrogen). The replacement of O with N allows the Si atom to becoordinated with O and N atoms in varying ratios. It is pointed out,however, that the total number of the coordinated atoms does not remainconstant, as 0 is replaced by N in composition (4), i.e., 1.5 O atomsreplace 1 N atom. In order for the number of coordinated atoms (O, N andC) to remain constant, the composition can be expressed as follows:

M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x±δ/2)N_(x∓δ-y)C_(y±δ/2):A   (4a)

In certain embodiments, the present invention is directed to a novelfamily of oxycarbonitride phosphors expressed by:

M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±3δ/2)N_(x∓δ-x)C_(z):A  (5)

wherein 0<x<12, 0≦y<x, 0<z<x, 0<x+y+z≦12, z<x+δ, and 0<δ<3. M(II)comprises at least one divalent cation, and may be selected from thegroup including Be, Mg, Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, Cd and otherdivalent transition metal ions. M(I) comprises at least one monovalentcation, and may be selected from the group including Li, Na, K, Rb, Cu,Ag and Au. M(III) comprises at least one trivalent cation, and may beselected from the group including B, Al, Ga, . In, Sc, Y, La and Gd, andother trivalent metal ions. A comprises a luminescence activator dopedin the crystal structure at a concentration level from about 0.001 mol %to about 20 mol %, preferably from about 0.1 mol % to about 10 mol %,relative to the total mol % of M(II) and M(I). A can be at least one ionselected from the group including Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho,Er, Tm, Yb, Lu, Mn, Bi, Sb, preferably Eu²⁺, Ce³⁺, Tb³⁺, Yb²⁺ and Mn²⁺.

In the phosphor of composition (5), O and N atoms can be exchanged withone another in a ratio of 1.5 (oxygen) to 1 (nitrogen), or 3δ/2 (oxygen)to δ (nitrogen). The replacement of O with N allows the Si atom to becoordinated with O and N atoms in varying ratios. However, the totalnumber of the coordinated atoms does not remain constant, as O isreplaced by N in composition (5), i.e., 1.5 O atoms replace 1 N atom. Inorder for the number of coordinated atoms (O, N and C) to remainconstant, the composition can be expressed as follows:

M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±δ/2)N_(x∓δ-2)N_(x∓δ-z)C_(z±δ/2):A  )5a)

In certain embodiments, the present invention is directed to a novelfamily of oxycarbonitride phosphors expressed by:

M(II)_(7-y)M(I))^(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±3δ/2)N_(x∓δ-z)C_(z)H_(v):A  (6)

wherein 0<x<12, 0≦y<1, 0<z<x, z<x+δ, 0 <δ≦3, 0≦v<1, and 0<x+y+z≦12.M(II) comprises at least one divalent cation, and may be selected fromthe group including Be, Mg, Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, Cd and otherdivalent transition metal ions. M(I) comprises at least one monovalentcation, and may be selected from the group including Li, Na, K, Rb, Cu,Ag and Au. M(III) comprises at least one trivalent cation, and may beselected from the group including B, Al, Ga, In, Sc, Y, La and Gd, andother trivalent metal ions. H comprises at least one monovalent anion,and may be selected from the group including F, Cl, Br and I. Acomprises a luminescence activator doped in the crystal structure at aconcentration level from about 0.001 mol % to about 20 mol %, preferablyfrom about 0.1 mol % to about 10 mol %, relative to the total mol % ofM(II) and M(I). A can be at least one ion selected from the groupincluding Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi,Sb, preferably Eu²⁺, Ce³⁺, Tb³⁺, Yb²⁺ and Mn²⁺.

In the phosphor of composition (6), oxygen and nitrogen atoms can beexchanged with one another in a ratio of 1.5 (oxygen) to 1 (nitrogen),or 3δ/2 (oxygen) to δ (nitrogen). The replacement of O with N allows theSi atom to be coordinated with O and N atoms in varying ratios. However,the total number of the coordinated atoms does not remain constant, as Ois replaced by N in composition (6), i.e., 1.5 O atoms replace 1 N atom.In order for the number of coordinated atoms (O, N and C) to remainconstant, the composition can be expressed as follows:

M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±δ/2-v/2)N_(x∓δ-z)C_(z±δ/2)H_(v):A.  (6a)

In certain embodiments, at least one of the phosphor compositions of thepresent invention is used as a wavelength converter for a light emittingdevice. The light emitting device has a first illuminant which emitslight in a wavelength range from about 300 nm to about 600 nm, and asecond illuminant which emits a visible light upon irradiation withlight from the first illuminant, wherein the second illuminant containsat least one phosphor of the present invention. The first illuminantcan, for example, emit light in a wavelength range from about 300 nm toabout 600 nm, preferably from about 400 nm to 550 nm, and morepreferably from about 420 nm to about 500 nm. In certain embodiments,the first illuminant is a laser diode or a light emitting diode (LED).When the second illuminant containing one or more phosphor compositionsof the invention is irradiated with light from the first illuminant, itcan, for example, emit light with a peak in wavelength range from about460 nm to about 660 nm, preferably from about 480 nm to about 600 nm,and more preferably from about 500 nm to about 590 nm.

In certain embodiments, the second illuminant comprises at least oneadditional phosphor. The additional phosphor or phosphors can, forexample, emit light having a peak in wavelength range from about 480 nmto about 660 nm, preferably from about 500 nm to about 650 nm, and morepreferably from about 520 nm to about 640 nm.

In the phosphor compositions of the present invention, luminescenceactivator A can be doped in the host crystal of the phosphor eithersubstitutionally or interstitially at a concentration level from about0.001 mol % to about 20mol % relative to the total mol % of therespective divalent and monovalent cations. In some embodiments, A isdoped in the crystal structure of the phosphor at a concentration levelfrom about 0.01 mol % to about 7 mol % relative to the total mol % ofthe divalent and monovalent cations. In other embodiments, A is doped inthe crystal structure of the phosphor at a concentration level fromabout 0.05 mol % to about 5 mol % relative to the total mol % of thedivalent and monovalent cations.

In certain embodiments, A comprises at least one co-activator. Theco-activator may be selected from, but not limited to, the groupincluding Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi,Sb, preferably Eu²⁺, Ce³⁺, Tb³⁺, Yb²⁺ and Mn²⁺, and the group includinghalogen anions, F, Cl, Br and I. The concentration level of theco-activator can be from about 0.001% to about 50% relative to theactivator.

In certain embodiments, the phosphor compositions of the presentinvention comprise at least one crystalline phase which is a tricliniccrystal system belonging to space group P1 (No. 1), an orthorhombiccrystal system, or another triclinic crystal system. In certainembodiments, the phosphor compositions of the present invention compriseat least two different crystalline phases selected from the following: atriclinic crystal system belonging to space group P1 (No. 1), anorthorhombic crystal system, and another triclinic system. In certainembodiments, it is possible that a crystalline phase can be classifiedas either orthorhombic or triclinic with similar certainty.

In certain embodiments, the phosphor compositions of the presentinvention maintain at least 70% of their relative emission intensity attemperatures up to 250° C. In other embodiments, the phosphorcompositions of the present invention maintain at least 85% of theirrelative emission intensity at temperatures up to 250° C. In otherembodiments, the phosphor compositions of the present invention maintainat least 90% of their relative emission intensity at temperatures up to250° C. In certain embodiments, the phosphor compositions of the presentinvention maintain at least 70% of their relative emission intensity attemperatures up to 200° C. In certain embodiments, the phosphorcompositions of the present invention maintain at least 85% of theirrelative emission intensity at temperatures up to 200° C. In otherembodiments, the phosphor compositions of the present invention maintainat least 90% of their relative emission intensity at temperatures up to200° C. In further embodiments, the phosphor compositions of the presentinvention maintain at least 90% of the relative emission intensity attemperatures up to 150° C. In other embodiments, the phosphorcompositions of the present invention maintain at least 95% of theirrelative emission intensity at temperatures up to 150° C.

In certain embodiments, the median diameter of the phosphor particles ofthe present invention can be from about 2 to about 50 microns,preferably from about 4 to about 30 microns, and more preferably fromabout 5 to about 20 microns. In some embodiments, the phosphor is agrain. In other embodiments, the phosphor is a particle.

In certain embodiments, the present invention further provides a lightemitting device comprising: a light source emitting light of wavelengthsfrom about 200 to about 600 nm, preferably from about 350 to about 490nm; and at least one phosphor of the present invention, where thephosphor is positioned to absorb at least a portion of the light outputfrom the light source and effectively modifies the color of the lightabsorbed from the light source, resulting in an emission of a longerwavelength than that of the light absorbed from the light source. Forexample, the phosphor compositions of the present invention can be mixedwith a silicone resin to form a slurry. The phosphor-filled silicone canbe applied to a LED chip as shown in FIGS. 20-23. The LED emits light inthe near ultraviolet (nUV) range (e.g., about 405 nm) or the blue range(e.g., about 450 nm).

The light source used in the present invention, can, for example,comprise a gallium nitride-based LED with a light-emitting layercomprising a quantum well structure. The light emitting device caninclude a phosphor of the present invention and a reflector located soas to direct light from the LED or the phosphor (see FIG. 20). Thephosphor of the present invention can be located on the surface of theLED (FIGS. 20 and 21) or separated therefrom (FIG. 22). The lightemitting device can further include a translucent material encapsulatingthe LED and the phosphor as seen in FIGS. 20-23.

In certain embodiments, the light emitting device of the presentinvention comprises a light source, such as a LED, to either createexcitation energy, or to excite another system to thereby provide theexcitation energy for the phosphor of the present invention. Devicesusing the present invention can include, for example, and withoutlimitation, white light producing light emitting devices, indigo lightproducing light emitting devices, blue light producing light emittingdevices, green light producing light emitting devices, yellow lightproducing light emitting devices, orange light producing light emittingdevices, pink light producing light emitting devices, red lightproducing light emitting devices, or light emitting devices with anoutput chromaticity defined by the line between the chromaticity of aphosphor of the present invention and that of at least one second lightsource. Headlights or other navigation lights for vehicles can be madewith the light emitting devices of the present invention. The lightemitting devices can be output indicators for small electronic devices,such as cell phones and personal digital assistants (PDAs). The lightemitting devices of the present invention also can be the backlights ofthe liquid crystal displays for TV, cell phones, PDAs and laptopcomputers. Luminaires for general illumination purpose can also be madewith the lighting devices of the present invention. Given appropriatepower supplies, room lighting can be based on devices of the invention.The warmth (i.e., amount of yellow/red chromaticity) of light emittingdevices of the present invention can be manipulated by selection of theratio of light from a phosphor of the present invention to light from asecond source (including, a second phosphor). Semiconductor lightsource-based white light devices can be used, for example, in aself-emission type display for displaying a predetermined pattern or agraphic design on a display portion of an audio system, a householdappliance, a measuring instrument, a medical appliance, and the like.Such semiconductor light source-based light devices also can be used,for example, and without limitation, as light sources of a back-lightfor a liquid crystal diode (LCD) display, a printer head, a facsimile, acopying apparatus, and the like.

Suitable semiconductor light sources for use in the present inventionalso are any that create light that excites the phosphor compositions ofthe present invention, or that excites a different phosphor that in turnexcites the phosphors of the present invention. Such semiconductor lightsources can be, for example, and without limitation, light sourcesincluding: GaN (gallium nitride) type semiconductor light sources;In-Al-Ga-N type semiconductor light sources, such asIn_(i)Al_(j)Ga_(k)N, where i+j+k=about 1, and where one or more of i, jand k can be 0; BN; SiC; ZnSe; B_(i)Al_(j)Ga_(k)N, where i+j+k=about 1,and where one or more of i, j, and k can be 0; andB_(i)In_(j)Al_(k)Ga_(l)N, where i+j+k +1=about 1, and where one or moreof i, j, be 0; and other such similar light sources. The semiconductorlight source (e.g., a semiconductor chip) can be based, for example, onIII-V or II-VI quantum well structures (meaning structures comprisingcompounds that combine elements of the periodic table of the chemicalelements from Group III with those from Group V or elements from GroupII with those from Group VI). In certain embodiments, a blue or a nearultraviolet (nUV) emitting semiconductor light source is used.

In certain embodiments, the phosphor compositions of the presentinvention can be excited by light from a primary light source, such as,for example, a semiconductor light source (e.g., a LED) emitting in thewavelength range of about 300 to about 500 nm, from about 350 nm toabout 480 nm or about 330 nm to about 390 nm, or from a secondary lightsource, such as, emissions from other phosphor(s) that emit in thewavelength range of about 300 nm to about 500 nm or about 350 nm toabout 420 nm. Where the excitation light is secondary, in relation tothe phosphor compositions of the present invention, theexcitation-induced light is the relevant source light. Devices that usethe phosphor compositions of the present invention can include, forexample, and without limitation, minors, such as, dielectric mirrors,which direct light produced by the phosphor compositions of the presentinvention to the light output, rather than direct such light to theinterior of the device (such as, the primary light source).

The light source (e.g., a LED) can, in certain embodiments, emit lightof at least about 200 nm, at least about 250 nm, at least about 255 nm,at least about 260 nm, and so on in increments of 5 nm up to at leastabout 600. In some embodiments, the light source emits light of over 600nm. The light source can, in certain embodiments, emit light of at mostabout 600 nm, at most about 595 nm, at most about 590 nm, and so on inincrements of 5 nm down to or less than about 200 nm. In someembodiments, the light source emits light at less than 200 nm. Incertain embodiments, the light source is a semiconductor light source.When LED chips are used, the LED chips are advantageously filled with atransparent encapsulant with a dome-like shape as shown in FIGS. 20-23.The encapsulant provides the mechanical protection on one hand, and theencapsulant further improves the optical property on the other hand(improved light emission of the LED die).

The phosphor composition may be dispersed in an encapsulant. By theencapsulant, the LED chips disposed on the substrate and a polymer lensare bonded without containing a gas as much as possible. The LED die canbe sealed directly by the encapsulant. However, it is also possible thatthe LED die is sealed with a transparent encapsulant (i.e., in thiscase, there are the transparent encapsulant and the encapsulant tocontain the phosphor composition). Owing to the refraction indices closeto each other, there is little loss of reflection at the interface.

In structural modifications, one or more LED chips are disposed on asubstrate in a reflection minor and the phosphor composition isdispersed in a lens disposed on the reflection mirror. Alternatively,one or more LED chips may be disposed on a substrate in a reflectionminor and the phosphor coated on the reflection minor.

In certain embodiments, the phosphor compositions of the presentinvention may be dispersed in an encapsulant such as silicone and epoxyresin. The phosphor-mixed encapsulant composition may be disposed on tothe LED chip which is mounted on a substrate. The structure of the LEDcombined with the phosphor-mixed encapsulant composition can be sealedby a transparent encapsulant as protective layer. In certainembodiments, the outer transparent encapsulant layer is shaped in a domeshape for directing and distributing the output light (FIGS. 20-23). Inan alternative device structure, one or more LED chips are amounted on asubstrate and the phosphor-mixed encapsulant composition is disposedonto the multiple-chip device (FIG. 23).

In certain embodiments, the phosphor compositions of the presentinvention can be dispersed in the light emitting device with a binder, asolidifier, a dispersant, a filler or the like. The binder can be, forexample, and without limitation, a light curable polymer, such as anacrylic resin, an epoxy resin, a polycarbonate resin, a silicone resin,a glass, a quartz and the like. The phosphor of the present inventioncan be dispersed in the binder by methods known in the art. For example,in some cases, the phosphor can be suspended in a solvent with thepolymer suspended, thus forming a phosphor-containing slurrycomposition, which then can be applied on the light emitting device andthe solvent evaporated therefrom. In certain embodiments, the phosphorcan be suspended in a liquid, such as, a pre-cured precursor to theresin to form a slurry, the slurry then can be dispersed on the lightemitting device and the polymer (resin) cured thereon. Curing can be,for example, by heat, UV, or a curing agent (such as, a free radicalinitiator) mixed with the precursor. As used herein “cure” or “curing”refers to, relates to or is a process for polymerizing or solidifying asubstance or mixture thereof, often to improve stability or usability ofthe substance or mixture thereof In certain embodiments, the binder usedto disperse the phosphor particles in a light emitting device can beliquefied with heat, thereby forming a slurry, and then the slurry isdispersed on the light emitting device and allowed to solidify in situ.Dispersants (meaning a substance that promotes the formation andstabilization of a mixture (e.g., a suspension) of one substance intoanother) include, for example, and without limitation, titanium oxides,aluminum oxides, barium titanates, silicon oxides, and the like.

In certain embodiments, at least one of the additional phosphors isselected from the following: (1) one or more phosphor compositions thatemit red light, including, for example and not limited to,Ca_(1-x)Sr_(x)S:Eu²⁺ (0≦x≦1), 3.5MgO.0.5MgF₂.GeO₂:Mn⁴⁺, Y₂O₂S:Eu³⁺,M₂Si₅N₈:Eu²⁺ (M=Ca, Sr, Ba), MAlSiN₃:Eu²⁺ (M=Ca, Sr), Y₂Si₄N₆C:Eu²⁺, andCaSiN₂:Eu²⁺, (2) one or more phosphor compositions that emit greenlight, including, for example and not limited to,Ca_(1-x)Sr_(x)Ga2S4:Eu²⁺ (0≦x≦1),Ca_(1-x−y−z)Mg_(x)Sr_(y)Ba_(z)SiO₄:Eu²⁺ (0≦x≦1, 0≦y≦1, 0≦z≦1, x+y+z≦1),BaMgAl₁₀O₁₇:Eu²⁺,Mn²⁺, MYSi₄N₇:Eu²⁺ (M=Ca, Sr, Ba), β-sialon:Eu²⁺,MSi₂O₂N₂:Eu²⁺ (M=Ca, Sr, Ba), Ba₃Si₆O₁₂N₂:Eu²⁺, M₂Si₅N₈:Ce³⁺ (M=Ca, Sr,Ba), Y₂Si₄N₆C:Ce³⁺, and α-sialon:Yb²⁺, (3) one or more phosphorcompositions that emit blue light, including, for example and notlimited to, (MSiO₃)_(m).(SiO₂)_(n):Eu²⁺, X (M=Mg, Ca, Sr, Ba; X═F, Cl,Br, I), where m is 1 or 0, and either (i) n>3 if m=1 or (ii) n=1 if m=0,MAl₂O₄:Eu²⁺ (M=Mg, Ca, Sr), and BaMgAl₁₀O₁₇:Eu²⁺, and (4) one or morephosphor compositions that emit yellow light, including, for example andnot limited to, Y₃Al₅O₁₂:Ce³⁺ (cerium-doped garnet type phosphor), anda-sialon:Eu²⁺.

In preferred embodiments, one or more additional phosphor compositionsare added to the phosphor compositions of the present invention to make,for example and without limitation, white light LED lamps. Thecompositions of such additional phosphors can be, Without limitation, asfollows:

(a) Ca_(1-x)Al_(x−xy)Si_(1-x+xy)N_(2-x−xy)C_(xy):A;

(b) Ca_(1x−z)Na_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A;

(c) M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A;

(d)M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2w/3)C_(xy)O_(w-v/2)H_(v):A;and

(e)M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2w/3-v/3)C_(xy)O_(w)H_(v):A;

wherein:

0<x<1, 0<y<1, 0≦z<1, 0≦v<1, 0<w<1, x+z<1, x>xy+z, v/2≦w,x−xy-2w/3-v/3<2, and 0<x−xy−z<1;

M(II) is at least one divalent cation;

M(I) is at least one monovalent cation;

M(III) is at least one trivalent cation;

H is at least one monovalent anion; and

A is a luminescence activator.

In the case that multiple phosphor compositions are used, it may beadvantageous that the multiple phosphor compositions are suspended ineach matrix, and, in that case, these matrices can be disposed back andforth in the light propagation direction. Thereby, the matrixconcentration can be reduced compared with the case that the differentphosphor compositions are dispersed and mixed together.

The present invention is not to be limited in scope by the specificembodiments in the following examples, which are intended only asexemplary illustrations of the invention. Indeed, various modificationsof the invention in addition to those shown and described herein willbecome apparent to those skilled in the art and are intended to fallwithin the scope of the appended claims.

EXAMPLES Preparation and Processes

For all examples described herein, the solid powders selected fromSrCO₃, CaCO₃, BaCO₃, 4MgCO₃.Mg(OH)₂.4H₂O or MgO, SrF₂, CaF₂, Li₂CO₃,AlN, Al₂O₃, Si₃N₄, SiO₂, SiC, and Eu₂O₃ were mixed in the designedratios specified in the following examples. The mixture was thenpulverized by ball milling or grinding for prolonged duration, e.g., 6hours, by dry or wet milling. The pulverized mixture was dried andsieved, and then loaded in a firing crucible. Subsequently, the mixturewas fired at 1300-1600° C. for 6-12 hours in inert or reducingatmosphere, e.g., forming gas (N₂/H₂) or N₂ in a high temperaturefurnace. After the firing, the product powder was cooled down to roomtemperature and ground and sieved.

Example 1 The Preparation of Phosphors Compositions of Family (1)

In this example, exemplary phosphor compositions of family (1),M(II)_(a)Si_(b)O_(c)N_(d)C_(e):A, are demonstrated, wherein M(II) is Sr;A is Eu²⁺; and 6.5<a<7.5, 8.5<b<12.5, 14<c<16, 6<d<7.5, and 0<e<1. Theexemplary preparations were conducted by firing the mixture of thestarting materials in the designed ratios listed in Table 1. Thephosphor compositions obtained by this process have the targetcompositions of oxycarbonitride expressed by sample numbers 1.1 and 1.2based on the starting amounts set forth in Table 1. The phosphorcompositions obtained are crystalline powders with a greenish-yellowbody color. The luminescence properties of the resultant phosphorcompositions are also listed in Tables 1A and 1B. Note that samples 1.1aand 1.1b are created with the same starting materials, but that sample1.1b was subjected to long-time annealing as further described below.

TABLE 1A The amount of starting materials (in grams) and luminescenceproperties of the resultant phosphor compositions of Example 1.Sr_(a)Si_(b)O_(c)N_(d)C_(e): Eu²⁺ Luminescence Characteristics Sample IDSrCO₃ SiC SiO₂ Si₃N₄ Eu₂O₃ QE, % λ_(em,) nm FWHM, nm 1.1a 2.2762 0.06760.4556 0.5910 0.0544 45.6 537 103 1.2 2.2762 0.0450 0.4387 0.7091 0.054453.7 537 103

TABLE 1B The amount of starting materials (in grams) and luminescenceproperties of the resultant phosphor compositions of Example 1 withlong-time annealing. Sr_(a)Si_(b)O_(c)N_(d)C_(e): Eu²⁺ LuminescenceCharacteristics Sample ID SrCO₃ SiC SiO₂ Si₃N₄ Eu₂O₃ QE, % λ_(em,) nmFWHM, nm 1.1b 2.2762 0.0676 0.4556 0.5910 0.0544 94 540 77

The phosphor materials were characterized by X-ray powder diffraction(XRD). The XRD pattern shows that this phosphor may be in onecrystalline phase or another depending on the heating conditions. Therepresentative XRD patterns for samples 1.1a and 1.1b are shown in FIG.1A and FIG. 1B, respectively. The XRD pattern shown in FIG. 1A indicatesthat the sample 1.1a contains mainly one crystalline phase which can beindexed to either an orthorhombic (STRUCTURE I) or a triclinic crystalsystem (STRUCTURE II). The observed X-ray powder diffraction data forsample 1.1a is listed in Table 2A. The unit cell parameters for theSTRUCTURE I and STRUCTURE II are summarized in Tables 2B and 2C. Withlong-time heating and annealing for an additional time of about 9-12hours at about 1100° C.-1300° C., this crystalline sample transformedinto another triclinic phase (STRUCTURE III) along with a small amountof strontium silicate phase, as shown in FIG. 1B. The observed XRD dataand unit cell parameters for the STRUCTURE III are summarized in Tables3A and 3B.

TABLE 2A The observed X-ray diffraction data of sample 1.1a. 2θ d (Å)I/I₀ (%) 12.972 6.8194 1.9 13.750 6.4348 1.2 17.316 5.1171 0.9 18.9904.6696 3.9 21.072 4.2127 9.9 24.208 3.6735 1.9 25.290 3.5187 15.3 26.2103.3973 47.3 27.669 3.2213 35.4 28.430 3.1368 100.0 29.471 3.0284 2.230.990 2.8834 1.8 32.130 2.7836 21.4 34.709 2.5824 8.3 35.872 2.501413.4 39.450 2.2823 7.9 40.150 2.2441 11.1 41.390 2.1797 2.0 42.0312.1479 9.7 42.970 2.1032 1.6 45.010 2.0125 38.1 45.669 1.9849 15.746.973 1.9328 2.7 48.150 1.8883 3.7 49.029 1.8565 2.7 49.590 1.8368 2.750.308 1.8122 3.4 51.230 1.7818 3.4 51.631 1.7689 3.5 52.310 1.7475 7.353.390 1.7147 7.9 54.210 1.6907 4.8 54.551 1.6809 7.2 56.910 1.6167 4.957.030 1.6136 5.2 57.350 1.6053 8.1 58.250 1.5826 4.9 59.111 1.5616 1.059.711 1.5473 2.9 62.191 1.4915 5.1 62.330 1.4885 4.9 62.852 1.4774 1.463.791 1.4579 1.4 65.130 1.4311 1.8 65.249 1.4288 1.7 67.689 1.3831 2.170.991 1.3266 2.8 71.149 1.3241 2.8 71.949 1.3113 3.6 73.551 1.2867 1.873.749 1.2837 2.7 75.708 1.2553 1.5 76.171 1.2488 2.1

TABLE 2B Crystal unit cell parameters of sample 1.1a indexed to anorthorhombic crystal system (STRUCTURE I). Crystal system: OrthorhombicLattice Parameters: a = 11.271 Å, b = 8.443 Å, c = 7.867 Å Unit cellvolume = 748.63 Å³

TABLE 2C Crystal unit cell parameters of sample 1.1a indexed to atriclinic crystal system (STRUCTURE II). Crystal system: Triclinic (P1)Lattice Parameters a = 11.249 Å, b = 8.431 Å, c = 7.862 Å α = 90.00° β =89.89° γ = 89.81° Unit cell volume = 765 Å³

TABLE 3A The observed X-ray powder diffraction data of sample 1.1bindexed to a triclinic crystal system (STRUCTURE III). 2θ d (Å) I/I₀ (%)(h k l) 12.570 7.0364 4.3 (0 1 0) 15.611 5.6720 1.1 (1 1 0) 17.7494.9931 2.8 (0 1 1) 20.130 4.4076 1.8 (−1 1 0) 23.027 3.8592 1.5 (1 −1 1)25.309 3.5162 32.6 (0 2 0) 25.952 3.4305 12.2 (1 2 0) 26.750 3.3300 21.6(1 0 2) 27.710 3.2168 23.4 (0 −1 2) 28.471 3.1324 11.0 (1 2 1) 28.8103.0964 9.2 (1 1 2) 29.750 3.0007 14.1 (−2 0 1) 30.249 2.9522 13.6 (−1 −12) 31.090 2.8743 46.2 (1 −1 2) 31.410 2.8457 25.7 (−1 2 0) 31.650 2.8247100.0 (−2 1 0) 32.889 2.7211 2.3 (−1 1 2) 34.350 2.6086 13.3 (−1 2 1)34.790 2.5766 3.0 (2 1 2) 35.531 2.5246 16.6 (1 2 2) 36.531 2.4577 0.9(−1 −2 2) 37.630 2.3884 29.7 (−2 0 2) 38.230 2.3523 3.8 (1 3 0) 39.0112.3070 13.6 (2 −1 2) 40.169 2.2431 1.0 (−1 −3 1) 40.930 2.2031 7.6 (03 1) 41.651 2.1667 2.8 (−3 −1 1) 41.968 2.1510 3.6 (3 2 0) 44.008 2.05592.7 (−1 3 0) 44.370 2.0400 8.3 (2 1 3) 45.009 2.0125 6.6 (−3 −2 1)46.089 1.9678 3.2 (0 2 3) 47.030 1.9306 5.7 (3 2 2) 48.050 1.8920 2.3 (23 2) 48.410 1.8788 6.7 (2 2 3) 48.990 1.8579 2.8 (−3 0 2) 49.610 1.83615.2 (3 −1 2) 50.310 1.8122 8.7 (3 3 1) 50.912 1.7921 3.8 (1 4 0) 51.6501.7683 10.2 (−3 −3 1) 52.271 1.7487 5.7 (4 1 0) 53.410 1.7141 5.2 (2 40) 54.253 1.6894 2.1 (3 3 2) 55.151 1.6640 13.0 (3 2 3) 57.171 1.60995.2 (1 4 2) 57.610 1.5987 5.9 (−1 4 0) 58.291 1.5816 9.6 (4 2 2) 59.4131.5544 1.9 (0 4 2) 59.711 1.5474 5.5 (3 4 1) 60.291 1.5339 1.2 (−2 −4 2)62.228 1.4907 1.1 (3 1 4) 62.910 1.4761 6.0 (4 1 3) 64.611 1.4413 2.5 (14 3) 66.427 1.4063 2.6 (2 5 0) 69.031 1.3594 4.1 (0 5 1) 69.650 1.34891.9 (4 3 3) 71.911 1.3119 3.9 (5 3 1) 73.910 1.2813 3.7 (1 4 4)

TABLE 3B Crystal unit cell parameters of sample 1.1b indexed to atriclinic crystal system (STRUCTURE III). Crystal system: TriclinicLattice Parameters: a = 7.03373 Å, b = 7.14537 Å, c = 7.28065 Å α =89.50°, β = 85.27°, γ = 76.72° Unit cell volume = 354.9 Å³

The luminescence excitation and emission spectra of samples 1.1a and1.1b are shown in FIGS. 2A and 2B, respectively. The luminescence isefficiently excited in a wavelength range of 410 nm to 490 nm, and theluminescence emission emits in the range of 510 nm to 600 nm, peaking atabout 540 nm. The thermal quenching characteristic of samples 1.1a and1.1b are shown in FIG. 3. It shows that the luminescence maintenance ofthe phosphor composition of sample 1.1 a at 150° C. is about 85% of thatat room temperature. At low temperatures, sample 1.1b exhibited aslightly better luminescence maintenance compared to sample 1.1a.However at temperatures above about 100° C., sample 1.1a exhibitedsuperior luminescence maintenance compared to sample 1.1b.

Example 2 The Preparation of Phosphor Compositions of Family (2) Example2a Sr₇Al_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y): Eu²⁺, (x+y=12)

To prepare the exemplary phosphor compositions of family (2),Sr₇Al_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y):Eu²⁺ (x+y=12), orSr₇Si₁₂O_(25-x)N_(x−y)C_(y):Eu²⁺, the starting materials were mixed indesigned ratios listed in Table 4. The samples were prepared byfollowing the preparation processes described above. The phosphorcompositions obtained by the process have the target compositions ofoxycarbonitride expressed by Sr₇Si₁₂O_(25-x)N_(x−y)C_(y):Eu²⁺ based onthe starting amounts set forth in Table 4 (see also FIG. 6). Thephosphor compositions obtained are crystalline powders with a green oryellow-green body color. The luminescence properties of the resultantphosphor compositions are also listed in Table 4.

TABLE 4 The amount of starting materials (in grams) and luminescenceproperties of the resultant phosphor compositions in Example 2a(Sr₇Al_(12−x−y)Si_(x+y)O_(25−x)N_(x−y)C_(y): Eu²⁺; x + y = 12).Sr₇Si₁₂O_(25−x)N_(x−y)C_(y): Eu²⁺ Luminescence Characteristics Sample IDSrCO₃ SiC SiO₂ Si₃N₄ Eu₂O₃ QE, % λ_(em,) nm FWHM, nm 2.1 2.2751 0.04500.4387 0.8666 0.0553 55.2 541 101 2.2 2.2751 0.0901 0.4724 0.7878 0.055358.3 541 99 2.3 2.3060 0.0904 0.4740 0.7905 0.0278 69.4 532 78 2.42.2751 0.0901 0.4724 0.7878 0.0553 75.2 534 104 2.5 2.2137 0.0895 0.46930.7826 0.1099 80.9 538 79 2.6 2.2137 0 0.4022 0.9391 0.1099 85 539 792.7 2.2137 0.0224 0.4190 0.9000 0.1099 87.3 541 79 2.8 2.2137 0.04470.4357 0.8608 0.1099 80 539 79 2.9 2.2137 0.0895 0.4692 0.7826 0.109980.9 538 79 2.10 2.2137 0.1342 0.5028 0.7043 0.1099 89.4 541 77 2.112.2137 0.1342 0.5028 0.7043 0.1099 79.2 537 107 2.12 2.2137 0.17890.5363 0.6261 0.1099 72.9 539 104 2.13 2.2137 0.2237 0.5698 0.54780.1099 76.8 538 80 2.14 2.2137 0.0895 0.4693 0.7826 0.1099 81 541 802.15 2.2751 0.0676 0.4555 0.5909 0.0553 63.1 536 106 2.16 2.2137 0.06710.4525 0.5869 0.1099 68.3 541 80 2.17 2.2137 0.0895 0.4693 0.4695 0.109955 538 112 2.18 2.2137 0.1342 0.5028 0.7043 0.1099 85.6 541 77 2.192.2137 0.1789 0.5363 0.6261 0.1099 69.7 540 76 2.20 2.2137 0.2237 0.56980.5478 0.1099 69.7 539 78 2.21 2.2137 0.2684 0.6033 0.4695 0.1099 76.2538 77

FIG. 4A shows the luminescence excitation and emission spectra of sample2.10. The XRD pattern for sample 2.10 that is shown in FIG. 4Bdemonstrates that this phosphor composition contains mainly onecrystalline phase. The diffraction patterns of exemplary sample 2.10 canbe indexed to a triclinic crystal system belonging to space group P1(No.1). The resultant unit cell parameters of sample 2.10 are summarizedin Table 5. This structure is similar to STRUCTURE III discussed above.

TABLE 5 Crystal structure parameters of sample 2.10 Crystal system:Triclinic Space group: P1 (No. 1) Density: 3.736 g/cm³; Z: 4 Unit cellvolume = 359.71 Å³ Lattice Parameters a = 7.1011(37) Å b = 7.2039(8) Å c= 7.2728(2) Å α = 88.931(4) β = 84.915(5) γ = 76.093(2)

The luminescence of sample 2.10 is efficiently excited in a wavelengthrange of about 410 nm to about 490 nm, and the luminescence emissionemits in the range of about 510 nm to about 600 nm, peaking at about 540nm. Compared with sample 1.1a, it is observed that the excitationprofile of sample 2.10 is different from that of sample 1.1a, and thatthe emission curve of sample 2.10 is also different from that of sample1.1. These facts indicate that the different crystalline structures leadto different luminescence properties between the sample 2.10 and thesample 1.1a. The thermal quenching profile of 2.10 is shown in FIG. 5.It shows that the luminescence maintenance at 150° C. of each sample isabout 90% of that at room temperature.

The exemplary samples of composition (2), 2.5, 2.7, 2.8, 2.9 and 2.13,contain mainly two phases, the STRUCTURE I (or STRUCTURE II) asdemonstrated in Example 1 and the STRUCTURE III demonstrated by thesample 2.10. These phosphor compositions have mainly two crystallinephases and contain varied content of carbon. It is noticed that theamount of the STRUCTURE I (or STRUCTRUE II) relative to that of theSTRUCTURE III is varied as the content of carbon changes in the seriesof 2.7, 2.8, 2.9 and 2.10, as shown by the XRD patterns in FIG. 6.Meanwhile, the peak of diffraction (−2 1 0) is shifted toward higher 2θangle as the content of carbon increases (FIGS. 7A and 7B), indicatingthe shrinkage of the lattice of the triclinic (P1) phase.

The luminescence emission spectra of exemplary samples of composition(2) are shown in FIG. 8. The phosphor compositions emit green oryellow-green light under blue or nUV light excitation. The thermalquenching characteristics of two samples, shown in FIG. 9, are nearlythe same at temperatures of 25-150° C., and become different attemperatures higher than 150° C. Compared to a phosphor having no carbonin its structure (e.g. 2.6), the phosphor composition having carbon inits structure (2.5) has a higher thermal stability.

Example 2b (Sr,Mg)₇Al_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y):Eu²⁺,(x+y=12)

The phosphors of composition(Sr,Mg),Al_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y):Eu²⁺ (x+y=12) or(Sr,Mg)₇Si₁₂O_(25-x)N_(x−y)C_(y):Eu²⁺), were prepared by the processesdescribed above. The starting materials were mixed in designed ratioslisted in Table 6. Compared with the composition of Example 2a, Mg hasbeen incorporated into the composition.

TABLE 6 The amount of starting materials (in grams) and luminescenceproperties of the resultant phosphor compositions in Example 2b((Sr,Mg)₇Al_(12−x−y)Si_(x+y)O_(25−x)N_(x−y)C_(y): Eu²⁺; x + y = 12).(Sr,Mg)₇Si₁₂O_(25−x)N_(x−y)C_(y): Eu²⁺ Luminescence CharacteristicsSample ID SrCO₃ SiC SiO₂ Si₃N₄ Eu₂O₃ MgO QE, % λ_(em,) nm FWHM, nm 3.12.1964 0.0453 0.3597 0.9349 0.1113 0.0122 87 541 77 3.2 2.1964 0.09060.3936 0.8557 0.1113 0.0122 96.3 541 76 3.3 2.1964 0.1359 0.4276 0.77640.1113 0.0122 85 541 77 3.4 2.1964 0.1812 0.4615 0.6972 0.1113 0.012283.6 543 76 3.5 2.1931 0.0904 0.4134 0.8386 0.1111 0.0122 89.9 541 763.6 2.1931 0.1809 0.4811 0.6804 0.1111 0.0122 87.6 542 76 3.7 2.18320.1351 0.5060 0.7088 0.1106 0.0122 80 542 76 3.8 2.1756 0.1353 0.50680.7099 0.1108 0.0152 78.7 541 77 3.9 2.1679 0.1355 0.5076 0.7111 0.11100.0183 71.1 543 77 3.10 2.1601 0.1357 0.5084 0.7122 0.1112 0.0214 73.7538 75 3.11 2.1524 0.1359 0.5092 0.7133 0.1114 0.0245 69.3 545 77 3.122.1832 0.0900 0.4722 0.7876 0.1106 0.0122 74 541 76 3.13 2.1756 0.09020.4730 0.7888 0.1108 0.0152 85.7 543 76 3.14 2.1679 0.0903 0.4737 0.79010.1110 0.0183 82.5 541 76 3.15 2.1601 0.0905 0.4745 0.7913 0.1112 0.021480.3 541 76 3.16 2.1524 0.0906 0.4753 0.7926 0.1114 0.0245 75.3 545 77

For the series of samples 3.1, 3.2, 3.3 and 3.4, the XRD patterns (seeFIG. 10) show that the each of the phosphor compositions contains mainlytwo phases, the orthorhombic and the triclinic phase, as observed inExample 1 and Example 2a, respectively. The diffractions from thetriclinic phase are shifted toward higher 2θ angles as the content ofcarbon increases in the composition, as typically shown by the peak (−21 0) in FIG. 11. This observation indicates shrinkage of the crystallattice as the content of carbon increases in the composition, and anaccompanying increase in oxygen content in the lattice.

FIG. 12 shows the thermal quenching profile of the luminesce emission ofsample 3.2. The lumen maintenance is about 95% at 150° C., indicating avery high lumen maintenance of this phosphor composition.

Example 2c (Sr,Mg)₇Al_(12-x−y))Si_(x+y)O_(25-x)N_(x−y)C_(y):Eu²⁺,(x+y=12)

The phosphors of composition(Sr,Mg)₇Al_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y):Eu²⁺, (x+y=12), or(Sr,Mg)₇Si₁₂O_(25-x)N_(x−y)C_(y):Eu²⁺, were prepared by the processesdescribed above. The raw materials were mixed in designed ratios listedin Table 7. Compared to the compositions of Examples 2a and 2b, thecontent of carbon is systematically altered in this Example 2c, whilemaintaining the content of oxygen from SiO₂ as constant in thecomposition.

TABLE 7 The amount of starting materials (in grams) and luminescenceproperties of the phosphors of Example 2c((Sr,Mg)₇Al_(12−x−y)Si_(x+y)O_(25−x)N_(x−y)C_(y): Eu²⁺; x + y = 12).(SrMg)₇Si₁₂O_(25−x)N_(x−y)C_(y): Eu²⁺ Luminescence CharacteristicsSample ID SrCO₃ SiC SiO₂ Si₃N₄ Eu₂O₃ MgO QE, % λ_(em,) nm FWHM, nm 4.12.1832 0.0000 0.4048 0.9451 0.1106 0.0122 85.5 541 77 4.2 2.1886 0.04510.4061 0.8945 0.1109 0.0122 85.5 539 77 4.3 2.1941 0.0905 0.4075 0.84370.1112 0.0122 76.1 538 77 4.4 2.1997 0.1361 0.4078 0.7935 0.1115 0.012370.9 541 76 4.5 2.2052 0.1819 0.4092 0.7422 0.1118 0.0123 68.2 541 76

The XRD patterns for these exemplary compositions are shown in FIG. 13.Similar to those of Example 2b, the XRD data show that each of thephosphors contains mainly two phases, the STRUCTURE I (orthorhombic) orSTRUCTURE II (triclinic), and the STRUCTURE III (triclinic). It is foundthat the amount of STRUCTURE III relative to that of the STRUCTURE I (orSTRUCTURE II) is varied as the content of carbon changes in the seriesof 4.1, 4.2, 4.3, 4.4 and 4.5, indicating an effect of carbon content onthe crystal structures. When the content of oxygen is fixed, thediffractions of the STRUCTURE III (−2 1 0) are shifted toward higher 2θangle (FIGS. 14A and 14B) as the content of carbon increases,corresponding to the lattice shrinkage due to the Si—C incorporation.

Example 3 The Preparation of Phosphor Compositions of Family (4)

The phosphors of compositionM(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x±3δ/2)N_(x∓δ-y)C_(y):A (M(II)=Sr,Ba, Ca; x+y=12) (or M(II)₇Si₁₂O_(25-x±3δ/2)N_(x±δ-y)C_(y):EU²⁺) wereprepared by the processes described above. The raw materials were mixedin designed ratios listed in Table 8. Compared with the compositions ofExamples 2, the ratio between nitrogen and oxygen in the preparations ofthis Example 3 is systematically altered by varying the amount of SiO₂and Si₃N₄ in the starting materials as well as the change of the type ofM(II).

TABLE 8 The amount of starting materials (in grams) and luminescenceproperties of the phosphor compositions of Example 3(M(II)₇M(III)_(12−x−y)Si_(x+y)O_(25−x±3δ/2)N_(x∓δ−y)C_(y): Eu²⁺; M(II) =Sr, Ba, Ca; x + y = 12). M(II)₇Si₁₂O_(25−x±3δ/2)N_(x∓δ−y)C_(y): Eu²⁺Luminescence Characteristics Sample ID SrCO₃ SiC SiO₂ Si₃N₄ Eu₂O₃ QE, %λ_(em,) nm FWHM, nm 5.1 2.2137 0.0895 0.4693 0.7826 0.1099 85.6 541 775.2 2.2137 0.1342 0.5028 0.7043 0.1099 69.7 540 76 5.3 2.2137 0.17890.5363 0.6261 0.1099 69.7 539 78 5.4 2.2137 0.2237 0.5698 0.5478 0.109976.2 538 77 5.5 2.2137 0.2684 0.6033 0.4695 0.1099 51.1 541 77 5.62.2269 0.0900 0.3911 0.8502 0.1106 82.2 542 77M(II)₇Si₁₂O_(25−x±3δ/2)N_(x∓δ−y)C_(y): Eu²⁺ Luminescence CharacteristicsSample ID BaCO₃ SiC SiO₂ Si₃N₄ Eu₂O₃ MgO QE, % λ_(em,) nm FWHM, nm 5.72.3702 0.0717 0.3759 0.6268 0.0881 0 81.5 495 39 5.8 2.2343 0.07510.3937 0.6565 0.0922 0.0507 40.6 494 47M(II)₇Si₁₂O_(25−x±3δ/2)N_(x∓δ−y)C_(y): Eu²⁺ Luminescence CharacteristicsSample ID CaCO₃ SiC SiO₂ Si₃N₄ Eu₂O₃ MgO QE, % λ_(em,) nm FWHM, nm 5.91.9686 0.1174 0.6155 1.0265 0.1442 0 33.1 563 93 5.10 1.7903 0.11860.6219 1.0372 0.1457 0.0801 36.9 561 91

The temperature dependencies of the emission intensity for samples 5.1,5.6, and 3.5 are illustrated in FIG. 15. The luminous maintenance athigh temperatures, e.g., 150° C., increases as the ratio of N/Oincreases. This demonstrates that the N/O ratio in the composition has aclear effect on the thermal stability of the luminescence emission inthe high temperature range. The excitation and emission spectra forsample 5.9 is shown in FIG. 16, and its reflection spectrum is shown inFIG. 17. The excitation and emission spectra for sample 5.7 is shown inFIG. 18, and its reflection spectrum is shown in FIG. 19. As shown inFIG. 18, sample 5.7 has a narrow bandwidth compared to other exemplarysamples of the invention, about 39 nm, where most other samples have abandwidth of between about 70 and 80 nm. It is also noted that sample5.7 peaks at less than 500 nm.

Example 4 The Preparation of Phosphor Compositions of Family (6)

The phosphors of compositionM(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±3δ/2-v/2)N_(x∓δ-z)C_(z)H_(v):A,where M(II)=Sr, M(I)=Li, M(III)=Al, H═F, and A=Eu²⁺, (orSr_(7-y)Li_(y)Al_(12-x−y−z)Si_(x+y+z)O_(25-x±3δ/2-v/2)N_(x∓δ-z)C_(z)F_(v):Eu²⁺)were prepared by the processes described above. The raw materials weremixed in designed ratios listed in Table 9. In this composition,monovalent metal Li and monovalent anion F are incorporated into thecomposition.

TABLE 9 The amount of starting materials (in grams) and luminescenceproperties of the phosphors of Example 4.Sr_(7−y)Li_(y)Al_(12−x−y−z)Si_(x+y+z)O_(25−x±3δ/2−v/2)N_(x) ∓_(δ−z)C_(z)F_(v): Eu²⁺ Luminescence Characteristics Sample ID SrCO₃ AlNSiO₂ Si₃N₄ Li₂CO₃ Eu₂O₃ SrF₂ SiC QE, % λ_(em,) nm FWHM, nm 6.1 2.27360.0074 0.4139 0.8757 0.0017 0.0548 0.0035 0.0506 36 538 76 6.2 2.27920.0074 0.4149 0.8261 0.0017 0.0549 0.0035 0.0952 37.3 541 77

Example 5 Preparation of pcLEDs Example 5a Green-Emitting PhosphorComposition Combined with Blue-Emitting LED

A green-emitting oxycarbonitride phosphor composition of the presentinvention, sample 3.2, was applied onto a blue-emitting LED chip in thedesign shown in FIG. 21. The phosphor composition was mixed with asilicone resin (silicone, Shin-Etsu LPS-2511). The phosphor-filledencapsulant composition was then injected onto an AlGaN-based,blue-emitting LED chip followed by a curing treatment according to themanufacturer's curing schedule. The emission spectra of the pcLED atdifferent operating currents are shown in FIG. 24.

Example 5b Green-Emitting Phosphor Composition Combined with aRed-Emitting Phosphor and a Blue-Emitting LED

A green-emitting oxycarbonitride phosphor composition of the presentinvention, sample 3.2, was combined with a second red-emitting phosphorcomposition (expressed byCa_(0.62)Eu_(0.0034)Na_(0.0235)Sr_(0.013)Al_(0.237)B_(0.0255)Si_(0.562)N_(1.94)C_(0.0875))to produce white light. The phosphor composition blend was mixed with asilicone resin and was applied to a blue-emitting LED chip by followingthe procedure described in Example 5a. The luminance properties of theresultant pcLED are displayed in FIG. 25. The emission spectrum of thepcLED is given in FIG. 26. This particular embodiment of phosphorcomposition blend of the instant invention gives a warm white light andits chromaticity coordinates lie very close to the black body locus witha correlated color temperature (CCT) of ˜2800 K and color renderingindex (CRI) of 94.

1. A composition comprising a phosphor having the formulaM(II)_(a)Si_(b)O_(c)N_(d)C_(e):A, wherein: 6<a<8, 8<b<14, 13<c<17,5<d<9, and 0<e<2; M(II) comprises at least one divalent cation; and Acomprises a luminescence activator doped in the host crystal of thephosphor.
 2. The composition of claim 1, wherein M(II) comprises atleast one divalent cation selected from the group consisting of Be, Mg,Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, and Cd.
 3. The composition of claim 1,wherein M(II) comprises two or more different divalent cations:
 4. Thecomposition of claim 1, wherein A comprises a luminescence activatorselected from the group consisting of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb, Lu, Mn, Bi, and Sb.
 5. The composition of claim 1,wherein A is doped in the host crystal of the phosphor at theconcentration level of 0.001 mol % to 20 mol % relative to M(II).
 6. Thecomposition of claim 1, wherein the phosphor comprises a firstcrystalline phase.
 7. The composition of claim 6, wherein the firstcrystalline phase is an orthorhombic crystal system or a tricliniccrystal system.
 8. The composition of claim 7, wherein the phosphor doesnot comprise any other crystalline phase.
 9. The composition of claim 1,wherein the phosphor comprises at least a first crystalline phase and asecond crystalline phase.
 10. The composition of claim 9, wherein thefirst crystalline phase is an orthorhombic crystal system and the secondcrystalline phase is a triclinic crystal system belonging to space groupP1 (No. 1).
 11. The composition of claim 9, wherein the firstcrystalline phase is a triclinic crystal system and the secondcrystalline phase is a triclinic crystal system belonging to space groupP1 (No. 1).
 12. The composition of claim 1, wherein the phosphorcomprises a crystalline phase that is an orthorhombic crystal system,wherein: the unit cell parameter a of the host crystal is from about11.071 Å to about 11.471 Å; the unit cell parameter b of the hostcrystal is from about 8.243 Å to about 8.643 Å; and the unit cellparameter c of the host crystal is from about 7.667 Å to about 8.067 Å.13. The composition of claim 1, wherein the phosphor comprises acrystalline phase that is a triclinic crystal system, wherein: the unitcell parameter a of the host crystal is from about 11.049 Å to about11.449 Å; the unit cell parameter b of the host crystal is from about8.231 Å to about 8.631 Å; the unit cell parameter c of the host crystalis from about 7.662 Å to about 8.062 Å; the unit cell parameter α of thehost crystal is from about 87 degrees to about 93 degrees; the unit cellparameter β of the host crystal is from about 87 degrees to about 93degrees; and the unit cell parameter γ of the host crystal is from about87 to about 93 degrees.
 14. The composition of claim 1, furthercomprising one or more additional phosphors.
 15. The composition ofclaim 1, further comprising at least one phosphor selected from thegroup consisting of: (a)Ca_(1-x)Al_(x−xy)Si_(1-x++xy)N_(2-x−xy)C_(xy):A; (b)Ca_(1-x−z)Na_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A; (c)M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A; (d)M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2w/3)C_(xy)O_(2-v/2)H_(v):A;and (e)M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2w/3)C_(xy)O_(w)H_(v):A;wherein: 0<x<1, 0<y<1, 0≦z<1, 0≦v<1, 0<w<1, x+z<1, x>xy+z, v/2≦w,x−xy-2w/3<2, and 0<x−xy−z<1; M(II) is at least one divalent cation; M(I)is at least one monovalent cation; M(III) is at least one trivalentcation; H is at least one monovalent anion; and A is a luminescenceactivator.
 16. A composition comprising a phosphor having the formulaM(II)₇Al_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y):A, wherein: 0<x≦12, 0<y<x,and 0<x+y≦12; M(II) comprises at least one divalent cation; and Acomprises a luminescence activator doped in the crystal structure. 17.The composition of claim 16, wherein M(II) comprises at least onedivalent cation selected from the group consisting of Be, Mg, Ca, Sr,Ba, Cu, Co, Ni, Pd, Zn, and Cd.
 18. The composition of claim 16, whereinM(II) comprises two or more different divalent cations.
 19. Thecomposition of claim 16, wherein A comprises a luminescence activatorthat is selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Gd,Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi, and Sb.
 20. The composition of claim16, wherein A is doped in the host crystal of the phosphor at theconcentration level of 0.001 mol % to 20 mol % relative to M(II). 21.The composition of claim 16, wherein the phosphor comprises acrystalline phase that is a triclinic crystal system belonging to spacegroup P1 (No. 1).
 22. The composition of claim 21, wherein the phosphordoes not comprise any other crystalline phases.
 23. The composition ofclaim 16, wherein the phosphor comprises at least a first crystallinephase and a second crystalline phase.
 24. The composition of claim 23,wherein the first crystalline phase is an orthorhombic crystal systemand the second crystalline phase is a triclinic crystal system belongingto space group P1 (No. 1).
 25. The composition of claim 23, wherein thefirst crystalline phase is a triclinic crystal system and the secondcrystalline phase is a triclinic crystal system belonging to space groupP1 (No. 1).
 26. The composition of claim 16, wherein the phosphorcomprises a crystalline phase that is a triclinic crystal systembelonging to space group P1 (No. 1), wherein the unit cell parameter αof the host crystal is from about 6.9011 Å to about 7.3011 Å; the unitcell parameter b of the host crystal is from about 7.0039 Å to about7.4039 Å; the unit cell parameter c of the host crystal is from about7.0728 Å to about 7.4728 Å; the unit cell parameter α of the hostcrystal is from about 85 degrees to about 92 degrees; the unit cellparameter β of the host crystal is from about 81 degrees to about 88degrees; and the unit cell parameter γ of the host crystal is from about72 degrees to about 79 degrees.
 27. The composition of claim 16, furthercomprising one or more additional phosphors.
 28. The composition ofclaim 16, further comprising at least one phosphor selected from thegroup consisting of: (a) Ca_(1-x)Al_(x−xy)Si_(1-x+xy)N_(2-x−xy)C_(xy):A;(b) Ca_(1-x−z)Na_(z)M(III)_(x−xy−z)Si_(1-x+y+z)N_(2-x−xy)C_(xy):A; (c)M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A; (d)M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2w/3)C_(xy)O_(2-v/2)H_(v):A;and (e)M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+y+z)N_(2-x−xy-2w/3-v/3)C_(xy)O_(w)H_(v):A;wherein: 0<x<1, 0<y<1, 0≦z<1, 0≦v<1, 0<w<1, x+z<1, x>xy+z, v/2≦w,x−xy-2w/3-v/3<2, and 0<x−xy−z<1; M(II) is at least one divalent cation;M(I) is at least one monovalent cation; M(III) is at least one trivalentcation; H is at least one monovalent anion; and A is a luminescenceactivator.
 29. A composition comprising a phosphor having a formulaselected from the group consisting of: (a)M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y):A, wherein 0<x≦12,0<x+y≦12, and 0<y<x; (b)M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x±3δ/2)N_(x∓δ-y)C_(y):A, wherein0<x<12, 0≦y<x, 0<x+y≦12, 0<δ<3, and δ<x+y; (c)M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x±δ/2)N_(x∓δ-y)C_(y±δ/2):A, wherein0<x<12, 0≦y<x, 0<x+y≦12, 0<δ≦3, and δ<x+y; (d)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±δ/2)N_(x∓δ-z)C_(z):A,wherein 0<x<12, 0≦y≦x, 0<z<x, 0<x+y+z≦12, z<x+δ, and 0<δ<3; (e)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±δ/2)N_(x∓δ-z)C_(z±δ/2):A,wherein 0<x<12, 0≦y<x, 0<z<x, 0<x+y+z≦12, z<x+δ, and 0<δ≦3; (f)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±3δ/2-v/2)N_(x∓δ-z)C_(z)H_(v):A,wherein 0<x<12, 0≦y<1, 0<z<x, z<x+δ, 0<δ≦3, 0≦v<1, and 0<x+y+z≦12; and(g)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±δ/2-v/2)N_(x∓δ-z)C_(z±δ/2)H_(v):A,wherein 0<x<12, 0≦y<1, 0<z<x, z<x+δ, 0<δ≦3, 0≦v<1, and 0<x+y+z≦12;wherein: M(II) comprises at least one divalent cation; M(I) comprises atleast one monovalent cation; M(III) comprises at least one trivalentcation; H comprises at least one monovalent anion; and A comprises aluminescence activator doped in the crystal structure.
 30. Thecomposition of claim 29, wherein: M(II) comprises at least one divalentcation selected from the group consisting of Be, Mg, Ca, Sr, Ba, Cu, Co,Ni, Pd, Zn, and Cd; M(III) comprises at least one trivalent cationselected from the group consisting of B, Al, Ga, In, Sc, Y, La and Gd;M(I) comprises at least one monovalent cation selected from the groupconsisting of Li, Na, K, Rb, Cu, Ag and Au; and H comprises at least onemonovalent anion selected from the group consisting of F, Cl, Br and I.31. The composition of claim 29, wherein A comprises at least oneluminescence activator selected from the group consisting of Ce, Pr, Nd,Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi, and Sb.
 32. Thecomposition of claim 29, wherein A is doped in the host crystal of thephosphor at the concentration level of 0.001 mol % to 20 mol % relativeto M(II) and M(I).
 33. The composition of claim 29, wherein the phosphorcomprises a crystalline phase that is a triclinic crystal systembelonging to space group P1 (No.1).
 34. The composition of claim 33,wherein the phosphor does not comprise any other crystalline phase. 35.The composition of claim 29, wherein the phosphor comprises at least afirst crystalline phase and a second crystalline phase.
 36. Thecomposition of claim 35, wherein the first crystalline phase is anorthorhombic crystal system and the second crystalline phase is atriclinic crystal system belonging to space group P1 (No. 1).
 37. Thecomposition of claim 35, wherein the first crystalline phase is atriclinic crystal system and the second crystalline phase is a tricliniccrystal system belonging to space group P1 (No. 1).
 38. The compositionof claim 29, further comprising one or more additional phosphors. 39.The composition of claim 29, further comprising at least one phosphorselected from the group consisting of: (a)Ca_(1-x)Al_(x−xy)Si_(1-x+xy)N_(2-x−xy)C_(xy):A; (b)Ca_(1-x−z)Na_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A; (c)M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A; (d)M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2w/3)C_(xy)O_(w-v/2)H_(v):A,and (e)M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2w/3-v/3)C_(xy)O_(w)H_(v):A;wherein: 0<x<1, 0<y<1, 0≦z<1, 0≦v<l, 0<w<1, x+z<1, x>xy+z, v/2≦w,x−xy-2w/3-v/3<2, and 0<x−xy−z<1; M(II) is at least one divalent cation;M(I) is at least one monovalent cation; M(III) is at least one trivalentcation; H is at least one monovalent anion; and A is a luminescenceactivator.
 40. A composition comprising a phosphor that comprises: atleast one carbon atom; at least one divalent cation M(II); at least oneoxygen atom; and at least one nitrogen atom; wherein the phosphorcomprises a first crystalline phase that is either an orthorhombiccrystal system or a triclinic crystal system.
 41. The composition ofclaim 40, wherein M(II) comprises at least one divalent cation selectedfrom the group consisting of Be, Mg, Ca, Sr, Ba, Cu, Co, Ni, Pd, Zn, andCd.
 42. The composition of claim 40, wherein the phosphor furthercomprises at least a second crystalline phase.
 43. The composition ofclaim 40, wherein the second crystalline phase is a triclinic crystalsystem belonging to space group P1 (No.1).
 44. The composition of claim43, wherein the phosphor emits light in a single emission spectrum fromabout 400 nm to about 600 nm.
 45. A light emitting device comprising: alight source emitting a first luminescence spectrum; a phosphorcomposition, which, when irradiated with light from the light source,emits light having a second luminescence spectrum; wherein the phosphorcomposition comprises at least one phosphor selected from the groupconsisting of: (a) M(II)_(a)Si_(b)O_(c)N_(d)C_(e):A, wherein 6<a<8,8<b<14, 13<c<17, 5<d−9, 0<e<2; (b)M(II)₇Al_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y):A, wherein 0<x≦12, 0<y<x,and 0<x+y≦12; (c) M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x)N_(x−y)C_(y):A,wherein 0<x≦12, 0<x+y≦12, and 0<y<x; (d)M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x≅3δ/2)N_(x∓δ-y)C_(y):A, wherein0<x<12, 0≦y<x, 0<x+y≦12, 0<δ≦3, and δ<x+y; (e)M(II)₇M(III)_(12-x−y)Si_(x+y)O_(25-x±δ/2)N_(x∓δ-y)C_(y±δ/2):A, wherein0<x<12, 0≦y<x, 0<x+y≦12, 0<δ≦3, and δ<x+y; (f)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±δ/2)N_(x∓δ-z)C_(z):A,wherein 0<x<12, 0≦y<x, 0<z<x, 0<x+y+z≦12, z<x+δ, and 0<δ≦3; (g)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±δ/2)N_(x∓δ/2)C_(z±δ/2):A,wherein 0<x<12, 0≦y<x, 0<z<x, 0<x+y+z≦12, z<x+δ, and 0<δ≦3; (h)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)Si_(x+y+z)O_(25-x±δ/2-v/2)N_(x∓δ-z)C_(z)H_(v):A,wherein 0<x12, 0≦y<1, 0<z<x, z<x+δ, 0<δ≦3, 0≦v<1, and 0<x+y+z≦12; and(i)M(II)_(7-y)M(I)_(y)M(III)_(12-x−y−z)O_(25-x±δ/2-v/2)N_(x∓δ-z)C_(z±δ/2)H_(v):A,wherein 0<x<12, 0≦y<1, 0<z<x, z<x+δ, 0<δ≦3, 0≦v<1, and 0<x+y+z≦12;wherein: M(II) comprises at least one divalent cation; M(I) comprises atleast one monovalent cation; M(III) comprises at least one trivalentcation; H comprises at least one monovalent anion; and A comprises aluminescence activator doped in the crystal structure.
 46. The lightemitting device of claim 45, wherein M(II) comprises at least onedivalent cation selected from the group consisting of Be, Mg, Ca, Sr,Ba, Cu, Co, Ni, Pd, Zn, and Cd; M(I) comprises at least one monovalentcation selected from the group consisting of Li, Na, K, Rb, Cu, Ag andAu; M(III) comprises at least one trivalent cation selected from thegroup consisting of B, Al, Ga, In, Sc, Y, La and Gd; H comprises atleast one anion selected from the group consisting of F, Cl, Br and I;and A comprises at least one luminescence activtor selected from thegroup consisting of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu,Mn, Bi, and Sb.
 47. The light emitting device of claim 45, wherein thefirst luminescence spectrum is from about 300 nm to about 600 nm. 48.The light emitting device of claim 45, wherein the first luminescencespectrum is from about 400 to about 550 nm.
 49. The light emittingdevice of claim 45, wherein the light source is a light emitting diodeor a laser diode.
 50. The light emitting device of claim 45, furthercomprising one or more additional phosphors.
 51. The light emittingdevice of claim 50, wherein the additional phosphor⁻emits redlight whenexcited by a light source.
 52. The light emitting device of claim 45,further comprising a second phosphor having a formula selected from thegroup consisting of (a) Ca_(1-x)Al_(x−xy)Si_(1-x+xy)N_(2-x−xy)C_(xy):A;(b) Ca_(1-x−z)Na_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A ; (c)M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A; (d)M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2w/3)C_(xy)O_(w-v/2)H_(v):A;and (e)M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy-2w/3-v/3)C_(xy)O_(w)H_(v):A;wherein: 0<x<1, 0<y<1, 0≦z<1, 0≦v<1, 0<w<1, x+z<1, x>xy+z, v/2≦w,x−xy-2w/3-v/3<2, and 0<x−xy−z<1; M(II) is at least one divalent cation;M(I) is at least one monovalent cation; M(III) is at least one trivalentcation; H is at least one monovalent anion; and A is a luminescenceactivator.
 53. The light emitting device of claim 45, further comprisingat least two additional phosphors.
 54. The light emitting device ofclaim 45, further comprising at least one additional phosphor that emitslight having a peak in wavelength range from about 480 to about 660 nm.55. The light emitting device of claim 45, further comprising at leastone additional phosphor that emits light having a peak in wavelengthrange from about 520 to about 640 nm.
 56. The light emitting device ofclaim 45, wherein the device emits white light.
 57. The light emittingdevice of claim 56, wherein the device emits cool white light.
 58. Thelight emitting device of claim 56, wherein the device emits warm whitelight.
 59. The light emitting device of claim 45, wherein the deviceemits green light having a wavelength value from about 480 nm to about600 nm.
 60. The light emitting device of claim 45, wherein the deviceemits light having a wavelength value from about 500 nm to about 590 nm.61. The light emitting device of claim 45, wherein the device emitslight having a wavelength value from about 380 nm to about 750 nm. 62.The light emitting device of claim 45, wherein the device emits lighthaving a wavelength value from about 400 nm to about 700 nm.
 63. Thelight emitting device of claim 45, further comprising at least onephosphor selected from the group consisting of Ca_(1-x)Sr_(x)S:Eu²⁺(0≦x≦1), 3.5MgO.0.5MgF₂.GeO₂:Mn⁴⁺, Y₂O₂S:Eu³⁺, M₂Si₅N₈:Eu²⁺ (M=Ca, Sr,Ba), MAlSiN₃:Eu²⁺ (M=Ca, Sr), Y₂Si₄N₆C:Eu²⁺, CaSiN₂:Eu²⁺,Ca_(1-x)Sr_(x)Ga₂S4:Eu²⁺ (0≦x≦1),Ca_(1-x−y−z)Mg_(x)Sr_(y)Ba_(z)SiO₄:Eu²⁺ (0≦x≦1, 0≦y≦1, 0≦z≦1, x+y+z≦1),BaMgAl₁₀O₁₇:Eu²⁺,Mn²⁺, MYSi₄N₇:Eu²⁺ (M=Ca, Sr, Ba), β-sialon:Eu²⁺MSi₂O₂N₂:Eu²⁺ (M=Ca, Sr, Ba), Ba₃Si₆O₁₂N₂:Eu²⁺, M₂Si₅N₈:Ce³⁺ (M=Ca, Sr,Ba), Y₂Si₄N₆C:Ce³⁺, α-sialon:Yb²⁺, (MSiO₃)_(m).(SiO₂)_(n):Eu²⁺, X (M=Mg,Ca, Sr, Ba; X═F, Cl, Br, I; m is 1 or 0, and either (i) n>3 if m=1 or(ii) n=1 if m=0), MAl₂O₄:Eu²⁺ (M=Mg, Ca, Sr), BaMgAl₁₀O₁₇:Eu²⁺,Y₃Al₅O₁₂:Ce³⁺ (cerium-doped garnet type phosphor), and α-sialon:Eu²⁺.